Macromolecular antioxidants based on dual type moiety per molecule: structures, methods of making and using the same

ABSTRACT

Disclosed are compounds represented by structural formula 
     
       
         
         
             
             
         
       
         
         
           
             methods of producing compounds represented by structural formula, and their use in inhibiting oxidation in an oxidizable material.

RELATED APPLICATION(S)

This application is a continuation of U.S. application Ser. No.16/372,594, filed Apr. 2, 2019, which is a divisional of U.S.application Ser. No. 15/038,361 filed May 20, 2016, which is a U.S.National Stage of International Application No. PCT/US2014/066935, filedNov. 21, 2014, which designates the U.S., published in English, andclaims the benefit of U.S. Provisional Application No. 61/907,863, filedon Nov. 22, 2013. The entire teachings of the above applications areincorporated herein by reference.

GOVERNMENT SUPPORT

This invention was made with government support under IIP-1138520 fromthe National Science Foundation. The government has certain rights inthe invention.

BACKGROUND OF THE INVENTION

Antioxidants are employed to prevent oxidation in a wide range ofmaterials, for example, plastics, elastomers, lubricants, bio- andpetroleum-based products (lubricants, gasoline, aviation fuels, andengine oils), cooking oil, cosmetics, processed food products, and thelike. While many small molecule antioxidants exist, there is acontinuing need for new antioxidants that have improved properties andthermal stability to function at high operating temperatures in a widerange of applications.

SUMMARY OF THE INVENTION

The present invention relates to compounds containing dualfunctionalities of aromatic amines and hindered phenols that can beuseful as stabilizers for organic materials, lubricants and petroleumbased products, plastics and elastomers, cosmetics, foods and cookingoils, and other materials. In particular, the present invention pertainsto highly effective antioxidant macromolecules described herein. Thisinvention also reports an improved, highly efficient and economicalprocess for the synthesis of amine (nitrogen) and sterically hinderedphenol containing dual functional macromolecules. The design ofmacromolecules in this invention can incorporate at least twoantioxidant moieties having different reactivities. The presentinvention also discloses their superior antioxidant performance comparedto presently used commercial antioxidants. This is demonstratedespecially in biobased lubricants and oils. In general one uniquefeature and design of the antioxidants described herein is theirimproved compatibility and performance in many oils and fuels includingbio-, petroleum- and synthetic oils and fuels such gasoline, diesel, andbiodiesel compared with currently available antioxidants.

The present invention pertains to a compound represented by structuralformula I:

wherein when j is 2, X is:

wherein R^(d) is —H or OH or an optionally substituted C1-C10 linear orbranched alkyl chain;

s is an integer from 1-10; and

wherein when j is 3, X is

and

wherein u is H or —CH₂CH₃, or C1-C10 linear or branched alkyl chain.

wherein A, for each occurrence independently, is selected from:

R^(d), independently for each occurrence, is —H, —OH, an optionallysubstituted C1-C10 linear or branched alkyl chain, e.g., a tertiarybutyl group.

[Y] is —(C═O)—, —(C═O)O—, —O(C═O)—, —O—, —S—, —NH—, —N(R)—

R_(c), independently for each occurrence, is H, a alkyl groupsubstituent bonded to a ring carbon atom adjacent (ortho) to a ringcarbon atom substituted with an —OH group. Each R, is H, independentlyan optionally substituted C1-C20 alkyl group, an optionally substitutedC1-C10 alkyl group, a tertiary carbon group, an optionally substitutedaryl group, and optionally substituted alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted alkoxycarbonylgroup, an optionally substituted aryloxycarbonyl group, —OH, —SH or —NH₂or an optionally substituted carbocyclic or heterocyclic non-aromaticring.

m is an integer from 0 to 2.

q is an integer from 0 to 10

R″, independently for each occurrence, is H, an optionally substitutedC1-C20 alkyl group, an optionally substituted C1-C10 alkyl group, anoptionally substituted aryl group, and optionally substituted alkoxygroup, an optionally substituted carbonyl group, an optionallysubstituted alkoxycarbonyl group, an optionally substitutedaryloxycarbonyl group, —OH, —SH or —NH₂ or an optionally substitutedcarbocyclic or heterocyclic non-aromatic ring.

R_(a), independently for each occurrence, is H, independently anoptionally substituted C1-C20 alkyl group, an optionally substitutedC1-C10 alkyl group, an optionally substituted aryl group, and optionallysubstituted alkoxy group, an optionally substituted carbonyl group, anoptionally substituted alkoxycarbonyl group, an optionally substitutedaryloxycarbonyl group, —OH, —SH or —NH₂ or an optionally substitutedcarbocyclic or heterocyclic non-aromatic ring.

n is an integer from 0 to 5.

Each R_(b), is H, independently an optionally substituted C1-C20 alkylgroup, an optionally substituted C1-C10 alkyl group, an optionallysubstituted aryl group, and optionally substituted alkoxy group, anoptionally substituted carbonyl group, an optionally substitutedalkoxycarbonyl group, an optionally substituted aryloxycarbonyl group,—OH, —SH or —NH₂ or an optionally substituted carbocyclic orheterocyclic non-aromatic ring.

n′ is an integer from 0 to 4.

In another embodiment, the present invention addresses relates to acompound represented by structural formula II.

wherein q is an integer from 0 to 10; in some instances, q is 0, in someinstances, q is 2; in some instances, q is 4;

R_(c) is a bulky alkyl group substituent bonded to a ring carbon atomadjacent (ortho) to a ring carbon atom substituted with an —OH group.Each R_(c) is H, independently an optionally substituted C1-C10 alkylgroup, a tertiary carbon group, an optionally substituted aryl group,and optionally substituted alkoxy group, an optionally substitutedcarbonyl group, an optionally substituted alkoxycarbonyl group, anoptionally substituted aryloxycarbonyl group, —OH, —SH or —NH₂ or anoptionally substituted carbocyclic or heterocyclic non-aromatic ring.

m is an integer from 0 to 2.

R″ is H, independently an optionally substituted C1-C10 alkyl group, anoptionally substituted aryl group, and optionally substituted alkoxygroup, an optionally substituted carbonyl group, an optionallysubstituted alkoxycarbonyl group, an optionally substitutedaryloxycarbonyl group, —OH, —SH or —NH₂ or an optionally substitutedcarbocyclic or heterocyclic non-aromatic ring.

Each R_(a), is H, independently an optionally substituted C1-C10 alkylgroup, an optionally substituted aryl group, and optionally substitutedalkoxy group, an optionally substituted carbonyl group, an optionallysubstituted alkoxycarbonyl group, an optionally substitutedaryloxycarbonyl group, —OH, —SH or —NH₂ or an optionally substitutedcarbocyclic or heterocyclic non-aromatic ring.

n is an integer from 0 to 5.

Each R_(b), is H, independently an optionally substituted C1-C10 alkylgroup, an optionally substituted aryl group, and optionally substitutedalkoxy group, an optionally substituted carbonyl group, an optionallysubstituted alkoxycarbonyl group, an optionally substitutedaryloxycarbonyl group, —OH, —SH or —NH₂ or an optionally substitutedcarbocyclic or heterocyclic non-aromatic ring.

n′ is an integer from 0 to 4.

In another embodiment, the present invention is a compound representedby structural formula III:

wherein each A is independently

q′ is an integer between 0 and 10; in some instances, q′ is 2; in someinstances, q′ is 3; in some instances, q′ is 4; in some instances, q is2; in some instances, q is 3; in some instances, q is 4; and

the remaining variables are as described in the immediately precedingparagraph or for structural formula (I).

In yet another embodiment, the present invention is a compoundrepresented by structural formula IV:

wherein each A is independently

q′ is an integer between 0 and 10; in some instances, q′ is 2; in someinstances, q′ is 3; in some instances, q′ is 4; in some instances, q is2; in some instances, q is 3; in some instances, q is 4; and

the remaining variables are as described in the immediately precedingparagraph or for structural formula (I).

In another embodiment, the present invention is a compound representedby structural formula V:

wherein in the variables are as described in the immediately precedingparagraph or structural formula (I). Each q independently is 2. Each qindependently is 3. Each q independently is 4.

In another embodiment, the present invention is a compound representedby structural formulas VI:

Where in the variables are as described in the immediately precedingparagraph or structural formula (I). Each q independently is 2. Each qindependently is 3. Each q independently is 4.

In another embodiment, the present invention is a method of producing acompound represented by structural formula (I). The method comprisescombining a linker, an amine and a phenol derivative in the presence ofcatalyst, wherein the phenol derivative comprises at least oneunsubstituted ring-carbon atom. In yet another embodiment, the presentinvention is a method of producing a compound represented structuralformula (I). The method comprises combining a phenolic-carbonylderivative represented by the following structural formula:

Wherein R_(c) is a bulky alkyl group substituent bonded to a ring carbonatom adjacent (ortho) to a ring carbon atom substituted with an —OHgroup. R is H, independently an optionally substituted C1-C10 alkylgroup, a tertiary carbon group, an optionally substituted aryl group,and optionally substituted alkoxy group, an optionally substitutedcarbonyl group, an optionally substituted alkoxycarbonyl group, anoptionally substituted aryloxycarbonyl group, an optionally substitutedcarbocyclic or heterocyclic non-aromatic ring. m is an integer from 0 to2. R* independently is H, NH, NH₂, Cl, or an optionally substitutedaryloxycarbonyl group, —OH, —SH or —NH₂ or an optionally substitutedcarbocyclic or heterocyclic non-aromatic ring. q is 0 to 10.

In another embodiment the present invention is a method of preventingoxidation in an oxidizable material, comprising combining the oxidizablematerial with a compound of the present invention.

The antioxidants described herein which are prepared by the disclosedprocesses in general are superior antioxidants (compared to currentlyavailable antioxidants) against oxidative, thermal degradation oforganic materials. These macromolecular antioxidants generally havecomparatively higher antioxidant activities along with improved thermalstability and performance in a wide range of materials including but notlimited to plastics; elastomers; thermo-plastic elastomers; lubricants;petroleum, bio- and synthetic oil based products (lubricants, gasoline,aviation fuels, and engine oils, biolubricants; metal working fluids,hydraulic fluids, drilling fluids, marine lubricants, environmentallyacceptable lubricants (EALs), grease, and bio- and synthetic-oil basedgrease); cooking oil; cosmetics; processed food products.

The processes of the present invention have many advantages which canallow improved synthesis of these macromolecular antioxidants. Forexample, the disclosed processes can be economically carried out in themelt phase without the presence of catalysts. Moreover, the processesdescribed herein generally reduce or eliminate purification steps forthe final product compared to existing syntheses, which can lead to asuperior performance/cost ratio for the product and reduced amounts ofwaste.

DETAILED DESCRIPTION OF THE INVENTION

A description of preferred embodiments of the invention follows.

As used herein, “dual functional” means any molecule with two functionalgroups which can optionally be the same or in certain embodiment aredifferent, such as amine and hydroxy.

As used herein “adduct” means chemically linked.

Sterically hindered, as used herein means that the substituent group(e.g., bulky alkyl group) on a ring carbon atom adjacent (or para) to aring carbon atom substituted with a phenolic hydroxy group (or thiol oramine group), is large enough to sterically hinder the phenolic hydroxygroup (or thiol or amine groups). This steric hindrance, in certainembodiments results in more labile or weak bonding between the oxygenand the hydrogen (or sulfur or nitrogen and hydrogen) and in turnenhances the stability and antioxidant activity (proton donatingactivity) of the sterically hindered antioxidant.

Repeat units of the antioxidants of the invention include substitutedbenzene molecules. Some of these benzene molecules are typically basedon phenol or a phenol derivative, such that they have at least onehydroxyl or ether functional group. In certain embodiments, the benzenemolecules have a hydroxyl group. The hydroxyl group can be a freehydroxyl group and can be protected or have a cleavable group attachedto it (e.g., an ester group). Such cleavable groups can be releasedunder certain conditions (e.g., changes in pH), with a desired shelflife or with a time-controlled release (e.g., measured by thehalf-life), which allows one to control where and/or when an antioxidantcan exert its antioxidant effect. The repeat units can also includeanalogous thiophenol and aniline derivatives, e.g., where the phenol —OHcan be replaced by —SH, —NH—, and the like.

Substituted benzene repeat units of an antioxidant of the invention arealso typically substituted with a bulky alkyl group or ann-alkoxycarbonyl group. In certain embodiments, the benzene monomers aresubstituted with a bulky alkyl group. In certain other embodiments, thebulky alkyl group is located ortho or meta to a hydroxyl group on thebenzene ring, typically ortho. A “bulky alkyl group” is defined hereinas an alkyl group that is branched alpha- or beta- to the benzene ring.In certain other embodiments, the alkyl group is branched alpha to thebenzene ring. In certain other embodiments, the alkyl group is branchedtwice alpha to the benzene ring, such as in a tert-butyl group. Otherexamples of bulky alkyl groups include isopropyl, 2-butyl, 3-pentyl, 1,1-dimethylpropyl, 1-ethyl-1-methylpropyl and 1, 1-diethylpropyl. Incertain other embodiments, the bulky alkyl groups are unsubstituted, butthey can be substituted with a functional group that does not interferewith the antioxidant activity of the molecule. Straight chainedalkoxylcarbonyl groups include methoxycarbonyl, ethoxycarbonyl,n-propoxycarbonyl, n-butoxycarbonyl and n-pentoxycarbonyl.N-propoxycarbonyl is a preferred group. Similar to the bulky alkylgroups, n-alkoxycarbonyl groups are optionally substituted with afunctional group that does not interfere with the antioxidant activityof the molecule.

The foregoing and other objects, features and advantages of theinvention will be apparent from the following more particulardescription of preferred embodiments of the invention, as illustrated inthe accompanying drawings in which like reference characters refer tothe same parts throughout the different views. The drawings are notnecessarily to scale, emphasis instead being placed upon illustratingthe principles of the invention.

In one embodiment the present invention is a compound represented bystructural formula (I) wherein the variables are as described asfollows:

wherein when j is 2, X is:

wherein R^(d) is —H or OH or an optionally substituted C1-C0 linear orbranched alkyl chain;

s is an integer from 1-10; and

wherein when j is 3, X is

and

wherein u is H or —CH₂CH₃, or C1-C10 linear or branched alkyl chain.

wherein A, for each occurrence independently, is selected from:

s is an integer from 0 to 10;

q is 0 to 10.

Each variable R^(d) is independently —H, —OH, an optionally substitutedC1-C10 linear or branched alkyl chain, e.g., a tertiary butyl group. uis H or —CH₂CH₃, or C1-C10 linear or branched alkyl chain.

[Y] is —(C═O)—, —(C═O)O—, —O(C═O)—, —O—, —S—, —NH—, —N(R)—

In one embodiment, each R″, R_(a), and R_(b) is H, independently anoptionally substituted C1-C20 alkyl group, an optionally substitutedC1-C10 alkyl group, an optionally substituted aryl group, an optionallysubstituted aralkyl, an optionally substituted alkoxy group, anoptionally substituted carbonyl group, an optionally substitutedalkoxycarbonyl group, an optionally substituted aryloxycarbonyl group,—OH, —SH or —NH₂ or an optionally substituted carbocyclic orheterocyclic non-aromatic ring. In another embodiment, each R″, R_(a)and R_(b) is independently an optionally substituted alkyl. In oneembodiment, each R″, R_(a), and R_(b) is independently a C1-C20 alkyl.In another embodiment, each R″, R_(a), and R_(b) is independently aC1-C10 alkyl. In another embodiment, each R″, R_(a) and R_(b) isindependently selected from the group consisting of:

Each R_(b) is independently an optionally substituted alkyl.

Each R_(c) is independently an optionally substituted alkyl or anoptionally substituted alkoxycarbonyl.

In another embodiment, each R_(c) is independently a C1-C10 alkyl. EachR_(c) is a bulky alkyl group substituent bonded to a ring carbon atomadjacent (ortho) to a ring carbon atom substituted with an —OH group.Each R_(c) is H, independently an optionally substituted C1-C10 alkylgroup, a tertiary carbon group, an optionally substituted aryl group,and optionally substituted alkoxy group, an optionally substitutedcarbonyl group, an optionally substituted alkoxycarbonyl group, anoptionally substituted aryloxycarbonyl group, —OH, —SH or —NH₂ or anoptionally substituted carbocyclic or heterocyclic non-aromatic ring. mis an integer from 0 to 2.

R″ is —H, an optionally substituted alkyl, an optionally substitutedaryl or an optionally substituted aralkyl. In one embodiment, R″ is —H,a C1-C20 alkyl or an optionally substituted aralkyl. In anotherembodiment, R″ is —H, a C1-C10 alkyl or a substituted benzyl group. Inyet another embodiment, R″ is —H. In yet another embodiment, R″ is:

In yet another embodiment, q is an integer from 0 to 10. In oneembodiment, q is an integer from 1 to 6. In another embodiment, q is 1.In yet another embodiment, q is 2. In yet another embodiment, q is 3. Inyet another embodiment, q is 4.

In yet another embodiment R″ is selected from the group consisting of:

In yet another embodiment, q is an integer from 0 to 10. In oneembodiment, q is an integer from 1 to 6. In another embodiment, q is 1.In yet another embodiment, q is 2. In yet another embodiment, q is 3. Inyet another embodiment, q is 4.

m is an integer from 0 to 2. In another embodiment m is 0. In oneembodiment, m is 1 or 2. In another embodiment, m is 1. In anotherembodiment, m is 2.

n is an integer from 0 to 5. In one embodiment n is 0. In yet anotherembodiment n is 1. In another embodiment n is 4. In one embodiment n is2. In another embodiment, n is 3 or 5.

n′ is an integer from 0 to 4. In one embodiment, n′ is 0; in anotherembodiment, n′ is 1; in another embodiment, n′ is 2; in anotherembodiment, n′ is 3; in another embodiment, n′ is 4.

In one embodiment of the present invention for the compounds representedby structural formula (II):

Each R_(a) is independently a C1-C20 alkyl. Each R_(c) is independentlya C1-C10 alkyl. R″ is —H, a C1-C20 alkyl or an optionally substitutedaralkyl, and the remainder of the variables are as described above forstructural formula (I).

In another embodiment, the compound of structural formula (II) isrepresented by structural formula (VII):

wherein the remainder of the variables is as described in theimmediately preceding paragraph or for structural formula (I).

In another embodiment, the compound of structural formula (II) isrepresented by structural formula (VIII):

wherein in R″ is as defined for Structural Formula (I); in someinstances, R″ is H or a C1-C10 alkyl.

In another embodiment, R″ in structural formula (VIII) is selected fromthe group of consisting of

In certain embodiments, the invention is a composition that is a mixtureof the compounds having Structures (VIII) with varying R″. In oneembodiment, the invention is a composition that is a mixture of thefollowing two structures:

In certain embodiments of the present invention the compoundsrepresented by structural formula (VIII) are represented by thefollowing structural formulas:

In yet other embodiments of the present invention the compoundsrepresented by structural formula (VIII) are represented by thefollowing structural formulas:

In another embodiment, the present invention is a compound or mixture ofcompounds represented by structural formula (VIII):

wherein R″ is

In yet other embodiments, the invention is a composition that is amixture of compounds with the following structures (i), (ii), (iii),(iv) and (v):

In certain embodiments, the present invention is a composition that is amixture of the compounds (i), (ii), (iii), (iv) in the following ratio:1:1:1:1; 0:1:1:1; 1:0:1:1; 1:1:0:1 or 1:1:1:0.

In certain embodiments, the present invention is a composition that is amixture of the compounds. The composition can include a mixture of twocompounds, such as the mixture of the following compounds: (i):(ii),(i):(iii), (ii):(iii), (ii):(iv), (iii):(iv), (v):(i), (v):(ii),(v):(iii), (v):(iv). As shown in Tables 1-9, each of these mixtures canbe presented in a ratio of 10:90, 20:80, 30:70, 40:60, 50:50, 60:40,70:30, 80:20, 90:10.

TABLE 1 i ii 10 90 20 80 30 70 40 60 50 50 60 40 70 30 80 20 90 10

TABLE 2 i iii 10 90 20 80 30 70 40 60 50 50 60 40 70 30 80 20 90 10

TABLE 3 ii iii 10 90 20 80 30 70 40 60 50 50 60 40 70 30 80 20 90 10

TABLE 4 ii iv 10 90 20 80 30 70 40 60 50 50 60 40 70 30 80 20 90 10

TABLE 5 iii iv 10 90 20 80 30 70 40 60 50 50 60 40 70 30 80 20 90 10

TABLE 6 v i 10 90 20 80 30 70 40 60 50 50 60 40 70 30 80 20 90 10

TABLE 7 v ii 10 90 20 80 30 70 40 60 50 50 60 40 70 30 80 20 90 10

TABLE 8 v iii 10 90 20 80 30 70 40 60 50 50 60 40 70 30 80 20 90 10

TABLE 9 v IV 10 90 20 80 30 70 40 60 50 50 60 40 70 30 80 20 90 10

In certain embodiments of the present invention is a composition that isa mixture of three compounds, such as the mixture of the followingcompounds (i):(ii):(iii), (ii):(iii):(iv), (iii):(iv):(i),(i):(ii):(iv). The ratio of these compounds in each of these mixtures islisted in Tables 10-28 below. Each of Tables 10-28 below describes therelative amounts of the different compounds. For example, Table 10 liststhe relative amounts of compounds (i):(ii):(iii); the relative amountsof compounds (ii):(iii):(iv); the relative amounts of compounds(iii):(iv)(i); and the relative amounts of compounds (i):(ii):(iv).

TABLE 10 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 10 80 2010 70 30 10 60 40 10 50 50 10 40 60 10 30 70 10 20 80 10 10 90 10 0 1000 0

TABLE 11 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 20 70 2020 60 30 20 50 40 20 40 50 20 30 60 20 20 70 20 10 80 20 0 90 0 10

TABLE 12 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 30 60 2030 50 30 30 40 40 30 30 50 30 20 60 30 10 70 30 0 80 0 20 90 0 10

TABLE 13 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 40 50 2040 40 30 40 30 40 40 20 50 40 10 60 40 0 70 0 30 80 0 20 90 0 10

TABLE 14 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 50 40 2050 30 30 50 20 40 50 10 50 50 0

TABLE 15 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 60 30 2060 20 30 60 10 40 60 0 50 0 50

TABLE 16 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 70 20 2070 10 30 70 0 40 0 60

TABLE 17 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 80 10 2080 0 30 0 70

TABLE 18 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 90 0 20 080

TABLE 19 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 0 100 0

TABLE 20 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 80 10 10 7010 20 60 10 30 50 10 40 40 10 50 30 10 60 20 10 70 10 10 80 0 10 90 0 0100

TABLE 21 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 70 20 10 6020 20 50 20 30 40 20 40 30 20 50 20 20 60 10 20 70 0 20 80 10 0 90

TABLE 22 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 60 30 10 5030 20 40 30 30 30 30 40 20 30 50 10 30 60 0 30 70 20 0 80 10 0 90

TABLE 23 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 50 40 10 4040 20 30 40 30 20 40 40 10 40 50 0 40 60 30 0 70 20 0 80 10 0 90

TABLE 24 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 40 50 10 3050 20 20 50 30 10 50 40 0 50 50

TABLE 25 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 30 60 10 2060 20 10 60 30 0 60 40 50 0 50

TABLE 26 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 20 70 10 1070 20 0 70 30 60 0 40

TABLE 27 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 80 10 0 8020 70 0 30

TABLE 28 Mixture i ii iii ii iii iv iii iv i i ii iv Ratio 10 90 10 80 020

In certain embodiments, the present invention is a composition that is amixture of compounds in the following ratio: (i):(ii) is 50:50.

In certain embodiments, the present invention is a composition that is amixture of compounds in the following ratio: (i):(iii) is 50:50.

In certain embodiments, the present invention is a composition that is amixture of compounds in the following ratio: (i):(iv) is 50:50.

In certain embodiments, the present invention is a composition that is amixture of compounds in the following ratio: (ii):(iii) is 50:50.

In certain embodiments, the present invention is a composition that is amixture of compounds in the following ratio: (ii):(iv) is 50:50.

In certain embodiments, the present invention is a composition that is amixture of compounds in the following ratio: (iii):(iv) is 50:50.

In certain embodiments, the present invention is a composition that is amixture of the following compounds: (v):(i), (v):(ii), (v):(iii),(v):(iv). Each of these mixtures can be present in a ratio of is 10:90,20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10.

In yet other embodiments of the present invention the compound isrepresented by the following structural formula:

In one embodiments, the present invention is represented by thefollowing structural formula:

In other embodiments, the present invention is represented by thefollowing structural formula:

In one embodiments, the present invention is represented by thefollowing structural formula:

In yet other embodiments, the present invention is represented by thefollowing structural formula:

In one embodiment, the present invention is represented by structuralformula (III):

wherein each A is independently selected from

and the remaining variables are as described in the immediatelypreceding paragraphs or structural formula (I). Each q, q′ independentlyis 2. Each q, q′ independently is 3. Each q, q′ independently is 4.

In yet another embodiment, the compounds of structural formula (III) arerepresented by the following structural formulas:

wherein R_(c) is a bulky alkyl group substituent bonded to a ring carbonatom adjacent (ortho) to a ring carbon atom substituted with an —OHgroup. Each R_(c) is H, independently an optionally substituted C1-C10alkyl group, a tertiary carbon group, an optionally substituted arylgroup, and optionally substituted alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted alkoxycarbonylgroup, an optionally substituted aryloxycarbonyl group, —OH, —SH or —NH₂or an optionally substituted carbocyclic or heterocyclic non-aromaticring. m is an integer from 0 to 2.

R″ is H, independently an optionally substituted C1-C10 alkyl group, anoptionally substituted aryl group, and optionally substituted alkoxygroup, an optionally substituted carbonyl group, an optionallysubstituted alkoxycarbonyl group, an optionally substitutedaryloxycarbonyl group, or an optionally substituted carbocyclic orheterocyclic non-aromatic ring.

Each R_(a), is H, independently an optionally substituted C1-C10 alkylgroup, an optionally substituted aryl group, and optionally substitutedalkoxy group, an optionally substituted carbonyl group, an optionallysubstituted alkoxycarbonyl group, an optionally substitutedaryloxycarbonyl group, —OH, —SH or —NH₂ or an optionally substitutedcarbocyclic or heterocyclic non-aromatic ring. n is an integer from 0 to5.

Each R_(b), is H, independently an optionally substituted C1-C10 alkylgroup, an optionally substituted aryl group, and optionally substitutedalkoxy group, an optionally substituted carbonyl group, an optionallysubstituted alkoxycarbonyl group, an optionally substitutedaryloxycarbonyl group, —OH, —SH or —NH₂ or an optionally substitutedcarbocyclic or heterocyclic non-aromatic ring. n′ is an integer from 0to 4.

In another embodiment, the compound of structural formula (III) isrepresented by structural formulas (IX):

wherein the remainder of the variables are as defined above.

In some embodiments of Structural Formula IX, q is an integer 1-8; inother embodiments, q is 1-4; in other embodiments, q is 2

In some embodiments of Structural Formula IX, R″ is a C1-C10 alkyl.

In another embodiment of Structural Formula IX, q is 3, where in R″ isH, a C1-C10 alkyl.

In another embodiment of Structural Formula IX, R″ is selected from thegroup of consisting of

In yet other embodiments, the compounds of structural formulas (IX) arerepresented by the following structural formulas:

In one embodiment, the present invention relates to compoundsrepresented by structural formulas (X):

wherein q is an integer from 1 to 8; in some embodiments, q is aninteger from 1 to 4; in some embodiments, q is 2;

R″ is C1-C10 alkyl;

q′ is an integer from 1 to 8; in some embodiments, q′ is an integer from2 to 6; in some embodiments, q′ is 2;

m is 2;

R_(c) is tertiary butyl group;

and n is 0.

In another embodiment, q and q′ are 2.

In another embodiment, R″ in structural formula (X) is selected from thegroup of consisting of

In yet another embodiment, the present invention is a compoundrepresented by structural formula IV

wherein each A is independently

and

the remaining variables are as described in the immediately precedingparagraph or structural formula (I). q, independently for eachoccurrence, is an integer from 1 to 10. Each q, q′ independently is 2.Each q, q′ independently is 3. Each q, q′ independently is 4.

In one embodiment, the compounds are represented by structural formulas(XI):

Wherein u is —H or —CH₂CH₃, q is an integer 1-8. q is 1-4. q ispreferably 3. R″ is C1-C10 alkyl. m is 2, R_(c) is tertiary butyl groupand n is 0, and R″ is selected from

In one embodiment of the present invention for the compounds representedby structural formulas (XII):

Wherein q is an integer 1-8. q is 1-4. q is preferably 2. R″ is C1-C10alkyl. q′ is 1-8. q′ is 2-6. Preferably q′ is 2. m is 2, R_(c) istertiary butyl group and n is 0,

In another embodiment q and q′ are 2; and R″ is a C1-C10 alkyl. Inanother embodiment, R″ in structural formula (XII) is selected from thegroup of consisting of

In yet other embodiments of the present invention the compoundsrepresented by structural formulas (XII) are represented by thefollowing structural formulas:

Wherein u is —H or —CH₂—CH₃, and R″ is selected from the group ofconsisting of

In yet other embodiments of the present invention the compoundsrepresented by structural formula (XIII):

Wherein q is an integer 1-8. q is 1-4. q is preferably 2. R″ is C1-C10alkyl. q′ is 1-8. q′ is 2-6. Preferably q′ is 2. m is 2, R_(c) istertiary butyl group and n is 0.

In another embodiment q and q′ are 2, where in R″ is a C1-C10 alkyl. Ris C1-10 alkyl chain, linear or branched. R is C2 to C6. Preferably R isC6 or C8 linear or branched carbon chain.

In yet other embodiments of the present invention the compoundsrepresented by structural formulas (XIII) are represented by thefollowing structural formulas:

Wherein u is —H or —CH₂—CH₃, R is C1-10 linear or branched alkyl chain,preferably C4 or C6 carbon linear or branched chain, and R″ is selectedfrom the group of consisting of

In another embodiment of the present invention the compounds representedby structural formula (XIV):

Wherein u is H or —CH₂—CH₃, R is C1-10 linear or branched alkyl chain,preferably C4 or C6 carbon linear or branched chain, and R″ is selectedfrom the group of consisting of

In certain embodiments, the antioxidant composition of the presentinvention comprising first antioxidant compound of Structural formula(I) and optionally a second antioxidant selected from the groupconsisting of: amine antioxidants, phenolic antioxidants, sulfurizedorganic compounds, organo-borate compounds, phosphite and phosphateantioxidants, copper compounds, zinc dithiodiphosphates, and phenolicantioxidants and/or aminic antioxidants.

In other embodiments, the weight ratio of the first antioxidant to thesecond antioxidant is 99:1 to 1:99.

In yet other embodiments, the weight ratio of the second antioxidant tothe first antioxidant is 1:1.

In other embodiments, the weight ratio of the second antioxidant to thefirst antioxidant is 1:1.

In other embodiments the weight ratio of the second antioxidant to thefirst antioxidant is 2:1 to 10:1.

In certain other embodiments of the present invention after combiningthe amine and amino-phenol derivative in a suitable solvent thecombination is refluxed at a temperature between 50 and 180° C., between90 and 130° C., between 100 and 110° C. In certain embodiments, thecombination is refluxed for between 1 and 48 hours, between 6 and 36hours, between 12 and 24 hours or between 18 and 20 hours.

In certain embodiments, in the methods of the present invention thesolvent is selected from the group consisting of toluene,tetrahydrofuran, acetonitrile, dichloromethane, methanol, ethanol andbutanol.

In certain embodiments of the present invention equimolar amounts of thephenol derivative and the amine are combined. In certain embodiments ofthe present invention the phenol derivative and the amine are combined a1:0.5, 1:1.2, 1:1.5, 1:1.0 molar ratio of phenol derivative:amine.

In one embodiment the above method can be conducted in one step and canbe conducted without catalyst. The process can be conducted by mixingtwo starting components in a suitable solvent and heating the reactionmixture to reflux.

In one embodiment, the above method involves mixing of stericallyhindered phenolic acid derivatives, preferably3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid with substitutedamines e.g., N-phenyl-1,4-phenylene-diamine in a suitable solvent. Thesolvent can be a single solvent or mixture of two solvents. In anotherembodiment, the solvent is toluene.

One embodiment of the present invention is directed to combiningequimolar amounts of the starting components, e.g.,3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid andN-phenyl-1,4-phenylene-diamine, in toluene and refluxing the reactionmixture at, e.g., 110° C.

In certain embodiment the methods of the present invention are simple,efficient, and economical and can be conducted without catalyst.

In certain other embodiments in the methods of the present invention,when solvent is used it can be recycled by separating the solvents fromthe reaction mixture using distillation.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives,3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic acid with substitutedamines e.g., N¹-isopropyl-N⁴-phenylbenzene-1,4-diamine in a suitablesolvent. The solvent can be a single solvent or mixture of two solvents.In another embodiment, the solvent is toluene.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives,3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid with substitutedamines e.g., N¹-(1,3-dimethylbutyl)-N⁴-phenylbenzene-1,4-diamine in asuitable solvent. The solvent can be a single solvent or mixture of twosolvents. In another embodiment, the solvent is toluene.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives,3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid with substitutedamines e.g., N¹-(1,4-dimethylpentyl)-N⁴-phenylbenzene-1,4-diamine in asuitable solvent. The solvent can be a single solvent or mixture of twosolvents. In another embodiment, the solvent is toluene.

In another embodiment, in the above method involves mixing of stericallyhindered phenolic acid derivatives,3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid with substitutedamines e.g N-sec-octyl-N′-phenyl-p-phenylenediamine in a suitablesolvent. The solvent can be a single solvent or mixture of two solvents.In another embodiment, the solvent is toluene.

In one embodiment, in the above method involves mixing of equimolaramounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid and mixture of atleast two amines selected from N-phenyl-1,4-phenylene-diamine;N¹-isopropyl-N⁴-phenylbenzene-1,4-diamine;N¹-(1,3-dimethylbutyl)-N⁴-phenylbenzene-1,4-diamine;N¹-(1,4-dimethylpentyl)-N⁴-phenylbenzene-1,4-diamine;N-sec-octyl-N′-phenyl-p-phenylenediamine in toluene and refluxing thereaction mixture at, e.g., 110° C.

In one embodiment, the above method involves mixing of stericallyhindered phenolic acid derivatives, preferably methyl3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate with substituted aminese.g., N-phenyl-1,4-phenylene-diamine in a suitable solvent. The solventcan be a single solvent or mixture of two solvents. In anotherembodiment, the solvent is toluene.

One embodiment of the present invention is directed to combiningequimolar amounts of the starting components, e.g., methyl3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate andN-phenyl-1,4-phenylene-diamine, in toluene and refluxing the reactionmixture at, e.g., 110° C.

In certain embodiment the methods of the present invention are simple,efficient, and economical and can be conducted without catalyst.

In certain other embodiments in the methods of the present invention,when solvent is used it can be recycled by separating the solvents fromthe reaction mixture using distillation.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives, methyl3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate with substituted aminese.g., N¹-isopropyl-N⁴-phenylbenzene-1,4-diamine in a suitable solvent.The solvent can be a single solvent or mixture of two solvents. Inanother embodiment, the solvent is toluene.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives methyl3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate with substituted aminese.g., N¹-(1,3-dimethylbutyl)-N⁴-phenylbenzene-1,4-diamine in a suitablesolvent. The solvent can be a single solvent or mixture of two solvents.In another embodiment, the solvent is toluene.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives,3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl chloride with substitutedamines e.g., N¹-(1,4-dimethylpentyl)-N⁴-phenylbenzene-1,4-diamine in asuitable solvent. The solvent can be a single solvent or mixture of twosolvents. In another embodiment, the solvent is toluene.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives,3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl chloride with substitutedamines e.g., N-sec-octyl-N′-phenyl-p-phenyenediamine in a suitablesolvent. The solvent can be a single solvent or mixture of two solvents.In another embodiment, the solvent is toluene.

In one embodiment, in the above method involves mixing of equimolaramounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl chloride and mixture of atleast two amines selected from N-phenyl-1,4-phenylene-diamine;N¹-isopropyl-N⁴-phenylbenzene-1,4-diamine;N¹-(1,3-dimethylbutyl)-N⁴-phenylbenzene-1,4-diamine;N¹-(1,4-dimethylpentyl)-N⁴-phenylbenzene-1,4-diamine;N-sec-octyl-N′-phenyl-p-phenyenediamine in toluene and refluxing thereaction mixture at, e.g., 110° C.

In one embodiment, the above method involves mixing of stericallyhindered phenolic acid derivatives, preferably3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl chloride with substitutedamines e.g., N-phenyl-1,4-phenylene-diamine in a suitable solvent. Thesolvent can be a single solvent or mixture of two solvents. In anotherembodiment, the solvent is toluene.

One embodiment of the present invention is directed to combiningequimolar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl chloride andN-phenyl-1,4-phenylene-diamine, in toluene and refluxing the reactionmixture at, e.g., 110° C.

In certain embodiment the methods of the present invention are simple,efficient, and economical and can be conducted without catalyst.

In certain other embodiments in the methods of the present invention,when solvent is used it can be recycled by separating the solvents fromthe reaction mixture using distillation.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives,3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl chloride with substitutedamines e.g., N¹-isopropyl-N⁴-phenylbenzene-1,4-diamine in a suitablesolvent. The solvent can be a single solvent or mixture of two solvents.In another embodiment, the solvent is toluene.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl chloride with substitutedamines e.g., N¹-(1,3-dimethylbutyl)-N⁴-phenylbenzene-1,4-diamine in asuitable solvent. The solvent can be a single solvent or mixture of twosolvents. In another embodiment, the solvent is toluene.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives,3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl chloride with substitutedamines e.g., N¹-(1,4-dimethylpentyl)-N⁴-phenylbenzene-1,4-diamine in asuitable solvent. The solvent can be a single solvent or mixture of twosolvents. In another embodiment, the solvent is toluene.

In yet another embodiment, in the above method involves mixing ofsterically hindered phenolic acid derivatives,3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl chloride with substitutedamines e.g., N-sec-octyl-N′-phenyl-p-phenyenediamine in a suitablesolvent. The solvent can be a single solvent or mixture of two solvents.In another embodiment, the solvent is toluene.

In one embodiment, in the above method involves mixing of equimolaramounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyl chloride and mixture of atleast two amines selected from N-phenyl-1,4-phenylene-diamine;N¹-isopropyl-N⁴-phenylbenzene-1,4-diamine;N¹-(1,3-dimethylbutyl)-N⁴-phenylbenzene-1,4-diamine;N¹-(1,4-dimethylpentyl)-N⁴-phenylbenzene-1,4-diamine;N-sec-octyl-N¹-phenyl-p-phenyenediamine in toluene and refluxing thereaction mixture at, e.g., 110° C.

In another embodiment of the present invention, a compound is formed byreacting a an amine represented by the following structural formula:

wherein R″ is selected from the group of consisting of

In another embodiment of the present invention, a mixture of compoundsis formed by reacting a mixture of amine selected from the compoundsrepresented by structural formula

wherein R″ is

Yet in another embodiment, R″ is represented by

In other embodiments of the present invention the linker [X] is acompound selected from ethane-1,2-diamine, ethane-1,2-diol,1,2-dichloro-ethane, butanedioic acid, [1,3,5]triazine-2,4,6-triol,propane-1,2,3-triol, trimethylolpropane, trichloromethylopropane,propane-1,2,3-triamine, 2,4,6-Trichloro-[1,3,5]triazine,3-carboxy-pentanedioic acid, 1,2,3-trichloro-propane

with phenol derivatives and amines (A) of Structures I-V

In certain other embodiments of the present invention the linker [X] isa compound selected from:

with phenol derivatives and amines (A) of Structures I-V

In certain other embodiments of the present invention after combiningthe amine and/or phenol derivatives and multifunctional linker in asuitbale solvent the combination is refluxed at a temperature between 0and 150° C., between 90 and 130° C., between 100 and 110° C. In certainembodiments, the combination is refluxed for between 1 and 48 hours,between 6 and 36 hours, between 12 and 24 hours or between 18 and 20hours. The linkers are di-, tri- or tetrafunctional to attach to amine,amine derivatives, phenol derivatives, e.g., diols, dichloro compounds(e.g., 1,2 dichloroethane, dichlorobutane), cyanuric chloride, cyanuricacid, triglycerol, trichlrogyecrol, trimethyl propane, or trichlorotrimethyl propane, pentaerythirtol, tetrachloropentaerythritol.

In certain embodiments, the linker for a compound represented by thefollowing structural formula:

wherein Z is OH or Cl, u is —H or —CH₂CH₃, or —C1-C10 linear or branchedalkyl chain, s is 1-10. R is —H or —OH or an optionally substitutedC1-C10 linear or branched alkyl chain.

In other embodiments the amines are represented by the followingstructural formula:

wherein:

each R_(a) is independently an optionally substituted alkyl;

each R_(b) is independently an optionally substituted alkyl;

R″ is independently —H or an optionally substituted alkyl; and

n is an integer from 0 to 5. n′ is an integer from 0 to 4.

In another embodiment, the phenol derivatives are represented by thefollowing structural formula:

wherein:

each R_(c) is independently an optionally substituted alkyl oralkoxycarbonyl;

R is —H, —OH, —OCH₃, —Cl, or an optionally substituted alkyl;

q is an integer from 0 to 10; and

m is 0 to 4.

In one embodiment, the solvent is selected from the group consisting ofmethanol, butanol, ethanol, tetrahydrofuran, acetone, acetonitrile,dichloromethane and toluene.

In yet other embodiments, the linker and phenol derivative are firstcombined in 1:1 or 1:2 or 1:3 molar ratios and the combination isrefluxed between 0 and 110° C. It is then followed by further additionof amine to the reaction in 0 or 1 or 2 molar ratio to the linker andrefluxed further to complete the reaction.

In other embodiment, the linker and amine are first combined in 1:1 or1:2 or 1:3 molar ratios and the combination is refluxed between 110° C.It is then followed by further addition of phenol derivative to thereaction in 0 or 1 or 2 molar ratio to the linker and refluxed furtherto complete the reaction.

One embodiment of the present invention is directed to combining 1:1 or2:1 or 3:1 or 4:1 molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol and/or amine tothe linker molecule, in toluene and refluxing the reaction mixture at,e.g., 110° C.

In yet other embodiment of the present invention is directed tocombining 3:1 molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol to the linkermolecule (e.g., cyanuric chloride), in toluene at 0-5° C.

In yet other embodiment of the present invention is directed tocombining 3:1 molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol to the linkermolecule (e.g., cyanuric chloride), in toluene at 40-65° C.

In yet another embodiment of the present invention is directed tocombining 3:1 molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol to the linkermolecule (e.g., cyanuric chloride), in toluene at 70-110° C.

In yet other embodiment of the present invention is directed tocombining 3:1 molar amounts of the starting components, e.gN-phenyl-1,4-phenylene-diamine to the linker molecule (e.g., cyanuricchloride), in toluene at 0-5° C.

In yet other embodiment of the present invention is directed tocombining 3:1 molar amounts of the starting components, e.gN-phenyl-1,4-phenylene-diamine to the linker molecule (e.g., cyanuricchloride), in toluene at 40-65° C.

In yet another embodiment of the present invention is directed tocombining 3:1 molar amounts of the starting components, e.gN-phenyl-1,4-phenylene-diamine to the linker molecule (e.g., cyanuricchloride), in toluene at 70-110° C.

One embodiment of the present invention is directed to combining 3:1molar amounts of the starting components, e.gN¹-isopropyl-N⁴-phenylbenzene-1,4-diamine,N¹-(1,3-dimethylbutyl)-N⁴-phenylbenzene-1,4-diamine,N¹-(1,4-dimethylpentyl)-N⁴-phenylbenzene-1,4-diamine andN-sec-octyl-N′-phenyl-p-phenyenediamine to the linker molecule (e.g.,cyanuric chloride), in toluene at 0-5° C., 40-65° C. and 70-110° C.separately.

One embodiment of the present invention is directed to combining 1:1molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol to the linkermolecule (e.g., cyanuric chloride), in toluene at 0-5° C.

In yet other embodiment of the present invention is directed tocombining 2:1 molar amounts of the starting components, e.gN-phenyl-1,4-phenylene-diamine to the linker molecule (e.g., cyanuricchloride), in toluene at 40-65° C.

In yet another embodiment of the present invention is directed tocombining 2:1 molar amounts of the starting components, e.gN-phenyl-1,4-phenylene-diamine to the linker molecule (e.g., cyanuricchloride), in toluene at 70-110° C.

One embodiment of the present invention is directed to combining 1:1molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol to the linkermolecule (e.g., cyanuric chloride), in toluene at 0-5° C.

In yet another embodiment of the present invention is directed tocombining 2:1 molar amounts of the starting components, e.gN¹-isopropyl-N⁴-phenylbenzene-1,4-diamine,N¹-(1,3-dimethylbutyl)-N⁴-phenylbenzene-1,4-diamine,N¹-(1,4-dimethylpentyl)-N⁴-phenylbenzene-1,4-diamine andN-sec-octyl-N′-phenyl-p-phenyenediamine to the linker molecule (e.g.,cyanuric chloride), in toluene at 40-65° C. and 70-110° C. separately.

One embodiment of the present invention, wherein linker and phenolderivative are first combined in 1:1 or 1:2 or 1:3 molar ratios and thecombination is refluxed between 0 and 110° C. It is then followed byfurther addition of amine to the reaction in 0 or 1 or 2 molar ratio tothe linker and refluxed further to complete the reaction.

In other embodiment, wherein linker and amine are first combined in 1:1or 1:2 or 1:3 molar ratios and the combination is refluxed between 110°C. It is then followed by further addition of phenol derivative to thereaction in 0 or 1 or 2 molar ratio to the linker and refluxed furtherto complete the reaction.

One embodiment of the present invention is directed to combining 1:1 or2:1 or 3:1 or 4:1 molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol and/or amine tothe linker molecule, in toluene and refluxing the reaction mixture at,e.g., 110° C.

In yet other embodiment of the present invention is directed tocombining 3:1 molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol to the linkermolecule (e.g., 1,2,3-Trichloro-propane), in toluene at 0-5° C.

In yet another embodiment of the present invention is directed tocombining 3:1 molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol to the linkermolecule (e.g., 1,2,3-Trichloro-propane), in toluene at 70-110° C.

In yet other embodiment of the present invention is directed tocombining 3:1 molar amounts of the starting components, e.gN-phenyl-1,4-phenylene-diamine to the linker molecule (e.g.,1,2,3-Trichloro-propane), in toluene at 0-5° C.

In yet another embodiment of the present invention is directed tocombining 3:1 molar amounts of the starting components, e.gN-phenyl-1,4-phenylene-diamine to the linker molecule (e.g.,1,2,3-Trichloro-propane), in toluene at 70-110° C.

One embodiment of the present invention is directed to combining 3:1molar amounts of the starting components, e.gN¹-isopropyl-N⁴-phenylbenzene-1,4-diamine,N¹-(1,3-dimethylbutyl)-N⁴-phenylbenzene-1,4-diamine,N¹-(1,4-dimethylpentyl)-N⁴-phenylbenzene-1,4-diamine andN-sec-octyl-N′-phenyl-p-phenyenediamine to the linker molecule (e.g.,1,2,3-Trichloro-propane), in toluene at 0-5° C. and 70-110° C.separately.

One embodiment of the present invention is directed to combining 2:1molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol to the linkermolecule (e.g., 1,2,3-Trichloro-propane), in toluene at 0-5° C.

In yet another embodiment of the present invention is directed tocombining 1:1 molar amounts of the starting components, e.gN-phenyl-1,4-phenylene-diamine to the linker molecule (e.g.,1,2,3-Trichloro-propane), in toluene at 70-110° C.

One embodiment of the present invention is directed to combining 2:1molar amounts of the starting components, e.g3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic alcohol to the linkermolecule (e.g., 1,2,3-Trichloro-propane), in toluene at 0-5° C.

In yet another embodiment of the present invention is directed tocombining 1:1 molar amounts of the starting components, e.gN¹-isopropyl-N⁴-phenylbenzene-1,4-diamine,N¹-(1,3-dimethylbutyl)-N⁴-phenylbenzene-1,4-diamine,N¹-(1,4-dimethylpentyl)-N⁴-phenylbenzene-1,4-diamine andN-sec-octyl-N′-phenyl-p-phenyenediamine to the linker molecule (e.g.,1,2,3-Trichloro-propane), in toluene at 40-65° C. and 70-110° C.separately.

The antioxidant compounds of the present invention can be employed toinhibit the oxidation of an oxidizable material, for example bycontacting the material with an antioxidant compound made by the methodsof the present invention.

For purposes of the present invention, a method of “inhibitingoxidation” is a method that inhibits the propagation of a freeradical-mediated process. Free radicals can be generated by heat, light,ionizing radiation, metal ions and some proteins and enzymes. Inhibitingoxidation also includes inhibiting reactions caused by the presence ofoxygen, ozone or another compound capable of generating these gases orreactive equivalents of these gases.

As used herein the term “oxidizable material” is any material which issubject to oxidation by free-radicals or oxidative reaction caused bythe presence of oxygen, ozone or another compound capable of generatingthese gases or reactive equivalents thereof. In particular theoxidizable material is a lubricant or a mixture of lubricants or fuel(including but not limited to gasoline, kerosene, diesel, biodiesel).The oxidizable material is a polyolefin, polymers, co-polymers,biopolymers, bioplastics, plastics, elastomers, thermoplastics polymers,polyamides, and blends thereof.

The shelf life of many materials and substances contained within thematerials, such as packaging materials, are enhanced by the presence ofthe antioxidants of the present invention. The addition of anantioxidant of the present invention to a packaging material is believedto provide additional protection to the product contained inside thepackage. In addition, the properties of many packaging materialsthemselves, particularly polymers, are enhanced by the presence of anantioxidant regardless of the application (i.e., not limited to use inpackaging). Common examples of packaging materials include paper,cardboard and various plastics and polymers. A packaging material can becoated with an antioxidant (e.g., by spraying the antioxidant or byapplying as a thin film coating), blended with or mixed with anantioxidant, or otherwise have an antioxidant present within it. In oneexample, a thermoplastic such as polyethylene, polypropylene orpolystyrene can be melted in the presence of an antioxidant in order tominimize its degradation during the polymer processing.

The lifetime of fuels (including but not limited to gasoline, kerosene,diesel, and biodiesel), lubricants, lubricant oils, mixtures thereof andcompositions comprising lubricants and lubricant oils in general can beimproved by contacting the lubricant, lubricant oil, mixtures thereof orcomposition comprising the lubricant or lubricant oil or mixturesthereof with compounds of the present invention, as described herein.

As used here, the terms “lubricants” and “lubricant oils” can be usedinterchangeably. Examples of lubricants suitable for use in thecompositions and methods of the present invention include, but are notlimited to: i) petroleum based oils (Group I, II and III), ii) syntheticoils (Group IV, V) and iii) biolubricant oils (vegetable oils such ascanola, soybean, high oleic canola, high oleic soybean oil, corn oiletc.). Group I oils, as defined herein are solvent refined base oils.Group II oils, as defined herein are modern conventional base oils madeby hydrocracking and early wax isomerization, or hydroisomerizationtechnologies and have significantly lower levels of impurities thanGroup I oils. Group III oils, as defined herein are unconventional baseoils. Groups I-III differ in impurities, and viscosity index as is shownin Kramer et al. “The Evolution of Base Oil Technology” TurbineLubrication in the 21^(st) Century ASTM STP #1407 W. R. Herguth and T.M. Wayne, Eds., American Society for Testing and Materials, WestConshohocken, Pa., 2001 the entire contents of which are incorporatedherein by reference. Group IV oils as defined herein are “synthetic”lubricant oils, including for example, poly-alpha olefins (PAOs).Biolubricants as defined herein are lubricants which contain at least51% biomaterial (see Scott Fields, Environmental Health Perspectives,volume 111, number 12, September 2003, the entire contents of which areincorporated herein by reference). Other examples of lubricant oils canbe found in Melvyn F. Askew “Biolubricants-Market Data Sheet” IENICA,August 2004 (as part of the IENICA work stream of the IENICA-INFORRMproject); Taylor et al. “Engine lubricant Trends Since 1990” paperaccepted for publication in the Proceedings I. Mech. E. Part J, Journalof Engineering Tribology, 2005 (Vol. 219 p 1-16); and Desplanches et al.“Formulating Tomorrow's Lubricants” page 49-52 of The Paths toSustainable Development, part of special report published in October2003 by Total; the entire contents of each of which are incorporatedherein by reference. Biolubricants are often but not necessarily, basedon vegetable oils. Vegetable derived, for example, from rapeseed,sunflower, palm and coconut can be used as biolubricants. They can alsobe synthetic esters which may be partly derived from renewableresources. They can be made from a wider variety of natural sourcesincluding solid fats and low grade or waste materials such as tallows.Biolubricants in general offer rapid biodegradability and lowenvironmental toxicity.

As used herein, Group I, II and III oils are petroleum base stock oil.The petroleum industry differentiates their oil based on viscosity indexand groups them as Group I, II and III. The synthetic oils are Group IVand Group V. In certain embodiments, synthetic oils are polyolesters forexample diesters, polyolesters such as neopentyl glycols (NPGs),trimethylolpropanes (TMPs), penterythritols (PEs), anddipentaerythritols (DiPEs). In other embodiments, synthetic oils includemonoesters and trimellitates. In other embodiments, synthetic oilsinclude polyalkylene glycols (PAGs). In certain embodiments of thepresent invention, 50% to 20% by weight of the antioxidants of thepresent invention are added to lubricant oils. In certain otherembodiments of the present invention, 10% to 5% by weight of theantioxidants of the present invention are added to lubricant oils. Incertain other embodiments of the present invention, 0.1% to 2% by weightof the antioxidants of the present invention are added to lubricantoils. In certain other embodiments of the present invention, 0.001% to0.5% by weight of the antioxidants of the present invention is added tolubricant oils. This percentage varies depending upon their endapplication and type of the base oil.

In certain embodiments of the present invention the antioxidants of thepresent invention are usually added to lubricant oils with stirring atbetween 0 and 100° C., between 20 and 80° C. or between 40-60° C.

In certain embodiments of the present invention the antioxidants of thepresent invention are usually added to lubricant and fuel oils (based onpetroleum, synthetic, and/or biobased oils) used in automotives andindustrial applications such as but not limited to transmission fluid,engine oil, break oil, metal working fluids, greases, gear oils.

In certain embodiments, the mixture of antioxidants of the presentinvention is preferred due to improved solubility characteristics ascompared to a single component antioxidant.

In yet other embodiments of the present invention the antioxidants ofthe present invention are usually added to lubricant and fuel oils alongwith other additional lubricant additives including but not limited toanti-corrosion, anti-foaming, viscosity modifier, pour pointdepressants, and other phenolic and aminic antioxidants.

In one embodiment, the present invention is a composition comprisingpresent invention antioxidant, and at least one additive selected fromthe group consisting of i) a surface additive; ii) a performanceenhancing additive; and iii) a lubricant protective additive.

In another embodiments the present invention is a lubricant compositioncomprising: a lubricant or a mixture of lubricants, a present inventionantioxidant and at least one additive selected from the group consistingof i) a surface additive; ii) a performance enhancing additive; and iii)a lubricant protective additive.

In yet another embodiment the present invention is a method of improvinga composition comprising combining the composition with presentinvention antioxidant; and at least one additive selected from the groupconsisting of i) a surface additive; ii) a performance enhancingadditive; and iii) a lubricant protective additive.

In yet another embodiment the present invention is a method of improvinga lubricant or a mixture of lubricants comprising combining thelubricant or mixture of lubricants with present invention antioxidant;and at least one additive selected from the group consisting of i) asurface additive; ii) a performance enhancing additive; and iii) alubricant protective additive.

The compositions and methods of the present invention generally provideincreased shelf life, increased oxidative resistance, enhancedperformance and/or improved quality to materials, such as, for example,lubricants and lubricant oils and fuels. In general it is believed thatbecause of the synergy of the antioxidants with the additives, thecompositions described herein have superior oxidation resistance. Theadditives exhibit several key functions such as corrosion inhibition,detergency, viscosity modification, antiwear performance, dispersantproperties, cleaning and suspending ability. The disclosed compositions,in general provide superior performance of lubricants in hightemperatures applications due to the presence of antioxidants which arethermally stable at high temperatures with enhanced oxidationresistance.

Stabilized Lubricant Oil Compositions

Lubricants, lubricant oils, mixtures thereof and compositions comprisinglubricants and lubricant oils can be improved by the methods of thepresent invention, by contacting the lubricant, lubricant oil, mixturesthereof or composition comprising the lubricant or lubricant oil ormixtures thereof with antioxidants, additives and mixtures thereof asdescribed herein.

As used here, the terms “lubricants” and “lubricant oils” can be usedinterchangeably. Examples of lubricants suitable for use in thecompositions and methods of the present invention include, but are notlimited to: i) petroleum based oils (Group I, II and III), ii) syntheticoils (Group IV and V)) and iii) biolubricant oils (vegetable oils suchas canola, soybean, corn oil etc.). Group I oils, as defined herein aresolvent refined base oils. Group II oils, as defined herein are modernconventional base oils made by hydrocracking and early waxisomerization, or hydroisomerization technologies and have significantlylower levels of impurities than Group I oils. Group III oils, as definedherein are unconventional base oils. Groups I-III differ in impurities,and viscosity index as is shown in Kramer et al. “The Evolution of BaseOil Technology” Turbine Lubrication in the 21^(st) Century ASTM STP#1407 W. R. Herguth and T. M. Wayne, Eds., American Society for Testingand Materials, West Conshohocken, Pa., 2001 the entire contents of whichare incorporated herein by reference. Group IV oils as defined hereinare “synthetic” lubricant oils, including for example, poly-alphaolefins (PAOs). Biolubricants as defined herein are lubricants whichcontain at least 51% biomaterial (see Scott Fields, Environmental HealthPerspectives, volume 111, number 12, September 2003, the entire contentsof which are incorporated herein by reference). Other examples oflubricant oils can be found in Melvyn F. Askew “Biolubricants-MarketData Sheet” IENICA, August 2004 (as part of the IENICA work stream ofthe IENICA-INFORRM project); Taylor et al. “Engine lubricant TrendsSince 1990” paper accepted for publication in the Proceedings I. Mech.E. Part J, Journal of Engineering Tribology, 2005 (Vol. 219 p 1-16); andDesplanches et al. “Formulating Tomorrow's Lubricants” page 49-52 of ThePaths to Sustainable Development, part of special report published inOctober 2003 by Total; the entire contents of each of which areincorporated herein by reference. Biolubricants are often but notnecessarily, based on vegetable oils. Vegetable derived, for example,from rapeseed, sunflower, palm and coconut can be used as biolubricants.They can also be synthetic esters which may be partly derived fromrenewable resources. They can be made from a wider variety of naturalsources including solid fats and low grade or waste materials such astallows. Biolubricants in general offer rapid biodegradability and lowenvironmental toxicity.

Additives

Examples of first additives suitable for use in the compositions andmethods of the present invention include but are not limited to, surfaceadditives, performance enhancing additives and lubricant protectiveadditives.

Surface additives: In certain embodiments of the present invention,surface additives can protect the surfaces that are lubricated fromwear, corrosion, rust, and frictions. Examples of these surfaceadditives suitable for use in the compositions and methods of thepresent invention include, but are not limited to: (a) rust inhibitors,(b) corrosion inhibitors, (c) extreme pressure agents, (d) tackinessagents, (e) antiwear agents, (f) detergents and dispersants, (g)compounded oil (like fat or vegetable oil to reduce the coefficient offriction without affecting the viscosity), (h) antimisting, (i) sealswelling agents and (j) biocides.

Performance Enhancing Additives: In certain embodiments of the presentinvention, performance enhancing additives improve the performance oflubricants. Examples of these performance enhancing additives suitablefor use in the Compositions and methods of the present inventioninclude, but are not limited to: (a) pour-point depressants, (b)viscosity index modifiers (c) emulsifiers, and (d) demulsifiers.

Lubricant Protective Additives: In certain embodiments of the presentinvention, lubricant protective additives maintain the quality of oilfrom oxidation and other thermal degradation processes. Examples ofthese lubricant protective additives suitable for use in thecompositions and methods of the present invention include, but are notlimited to: (a) oxidation inhibitors and (b) foam inhibitors.

Other Lubricant Additives

In certain embodiments, a second additive can be used in thecompositions and methods of the present invention in combination withthe first antioxidant and the first additive as described above.Examples of second additives suitable for use in the compositions andmethods of the present invention include, include but are not limitedto, for example, dispersants, detergents, corrosion inhibitors, rustinhibitors, metal deactivators, antiwear and extreme pressure agents,antifoam agents, friction modifiers, seal swell agents, demulsifiers,viscosity index improvers, pour point depressants, and the like. See,for example, U.S. Pat. No. 5,498,809 for a description of usefullubricating oil composition additives, the disclosure of which isincorporated herein by reference in its entirety.

Dispersants: Examples of dispersants suitable for use in thecompositions and methods of the present invention include, but are notlimited to: polybutenylsuccinic acid-amides, -imides, or -esters,polybutenylphosphonic acid derivatives, Mannich Base ashlessdispersants, and the like.

Detergents: Examples of detergents suitable for use in the compositionsand methods of the present invention include, but are not limited to:metallic phenolates, metallic sulfonates, metallic salicylates, metallicphosphonates, metallic thiophosphonates, metallic thiopyrophosphonates,and the like.

Corrosion Inhibitors: Examples of corrosion inhibitors suitable for usein the compositions and methods of the present invention include, butare not limited to: phosphosulfurized hydrocarbons and their reactionproducts with an alkaline earth metal oxide or hydroxide,hydrocarbyl-thio-substituted derivatives of 1,3,4-thiadiazole,thiadiazole polysulphides and their derivatives and polymers thereof,thio and polythio sulphenamides of thiadiazoles such as those describedin U.K. Patent Specification 1,560,830, and the like.

Rust Inhibitors: Examples of rust inhibitors suitable for use in thecompositions and methods of the present invention include, but are notlimited to: nonionic surfactants such as polyoxyalkylene polyols andesters thereof, anionic surfactants such as salts of alkyl sulfonicacids, and other compounds such as alkoxylated fatty amines, amides,alcohols and the like, including alkoxylated fatty acid derivativestreated with C9 to C16 alkyl-substituted phenols (such as the mono- anddi-heptyl, octyl, nonyl, decyl, undecyl, dodecyl and tridecyl phenols).

Metal Deactivators: Metal deactivators as used herein, are the additiveswhich form an inactive film on metal surfaces by complexing withmetallic ions and reducing, for example, the catalytic effect on metalgum formation and other oxidation. Examples of metal deactivatorssuitable for use in the compositions and methods of the presentinvention include, but are not limited to: N,N-disubstitutedaminomethyl-1,2,4-triazoles, N,N-disubstitutedaminomethyl-benzotriazoles, mixtures thereof, and the like.

Antiwear and Extreme Pressure Additives: Antiwear and extreme pressureadditives, as used herein, react with metal surfaces to form a layerwith lower shear strength then metal, thereby preventing metal to metalcontact and reducing friction and wear. Examples of antiwear additivessuitable for use in the compositions and methods of the presentinvention include, but are not limited to: sulfurized olefins,sulfurized esters, sulfurized animal and vegetable oils, phosphateesters, organophosphites, dialkyl alkylphosphonates, acid phosphates,zinc dialkyldithiophosphates, zinc diaryldithiophosphates, organicdithiophosphates, organic phosphorothiolates, organic thiophosphates,organic dithiocarbamates, dimercaptothiadiazole derivatives,mercaptobenzothiazole derivatives, amine phosphates, aminethiophosphates, amine dithiophosphates, organic borates, chlorinatedparaffins, and the like.

Antifoam Agents: Examples of antifoam agents suitable for use in thecompositions and methods of the present invention include, but are notlimited to: polysiloxanes and the like.

Friction Modifiers: Examples of friction modifiers suitable for use inthe compositions and methods of the present invention include, but arenot limited to: fatty acid esters and amides, organic molybdenumcompounds, molybdenum dialkylthiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiolates, copper oleate, coppersalicylate, copper dialkyldithiophosphates, molybdenum disulfide,graphite, polytetrafluoroethylene, and the like.

Seal Swell Agents: Seal swell agents, as used herein, react chemicallywith elastomers to cause slight swell thus improving low temperatureperformance especially in, for example, aircraft hydraulic oil. Examplesof seal swell agents suitable for use in the compositions and methods ofthe present invention include, but are not limited to: dioctyl sebacate,dioctyl adipate, dialkyl phthalates, and the like.

Demulsifiers: Demulsifiers, as used herein promote separation of oil andwater in lubricants exposed to water. Examples of demulsifiers suitablefor use in the compositions and methods of the present inventioninclude, but are not limited to: the esters described in U.S. Pat. Nos.3,098,827 and 2,674,619 incorporated herein by reference.

Viscosity Index Improvers: Examples of viscosity index improverssuitable for use in the compositions and methods of the presentinvention include, but are not limited to: olefin copolymers, dispersantolefin copolymers, polymethacrylates,vinylpyrrolidone/methacrylate-copolymers, polyvinylpyrrolidones,polybutanes, styrene/-acrylate-copolymers, polyethers, and the like.

Pour Point Depressants: Pour point depressants as used herein reduce thesize and cohesiveness of crystal structure resulting in low pour pointand increased flow at low-temperatures. Examples of pour pointdepressants suitable for use in the compositions and methods of thepresent invention include, but are not limited to: polymethacrylates,alkylated naphthalene derivatives, and the like.

Other Antioxidants and Stabilizers

In certain embodiments, a second antioxidant or a stabilizer can be usedin the compositions and methods of the present invention in combinationwith the first antioxidant and the first additive and optionally thesecond additive as described above. Examples of second antioxidantssuitable for use in the compositions and methods of the presentinvention include, include but are not limited to:

-   1. Amine Antioxidants-   1.1. Alkylated Diphenylamines, for example octylated diphenylamine;    styrenated diphenylamine; mixtures of mono- and dialkylated    tert-butyl-tert-octyldiphenylamines; and 4,4′-dicumyldiphenylamine.-   1.2. Phenyl Naphthylamines, for example N-phenyl-1-naphthylamine;    N-phenyl-2-naphthylamine; tert-octylated N-phenyl-1-naphthylamine.-   1.3. Derivatives of para-Phenylenediamine, for example    N,N′-diisopropyl-p-phenylenediamine;    N,N′-di-sec-butyl-p-phenylenediamine;    N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine;    N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine;    N,N′-bis(1-methylheptyl)-p-phenylenediamine;    N,N′-diphenyl-p-phenylenediamine;    N,N′-di-(naphthyl-2)-p-phenylenediamine;    N-isopropyl-N′-phenyl-p-phenylenediamine;    N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine;    N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine;    N-cyclohexyl-N′-phenyl-p-phenylenediamine;    N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine.-   1.4. Phenothiazines, for example phenothiazine;    2-methylphenothiazine; 3-octylphenothiazine;    2,8-dimethylphenothiazine; 3,7-dimethylphenothiazine;    3,7-diethylphenothiazine; 3,7-dibutylphenothiazine;    3,7-dioctylphenothiazine; 2,8-dioctylphenothiazine.-   1.5. Dihydroquinolines, for example    2,2,4-trimethyl-1,2-dihydroquinoline or a polymer thereof.-   2. Phenolic Antioxidants-   2.1. Alkylated monophenols, for example    2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butylphenol;    2-tert-butyl-4,6-dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol;    2,6-di-tert-butyl-4-n-butylphenol;    2,6-di-tert-butyl-4-isobutylphenol;    2,6-di-tert-butyl-4-sec-butylphenol;    2,6-di-tert-butyl-4-octadecylphenol;    2,6-di-tert-butyl-4-nonylphenol; 2,6-dicyclopentyl-4-methylphenol;    2-(P-methylcyclohexyl)-4,6-dimethylphenol;    2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol;    2,6-di-tert-butyl-4-methoxymethylphenol;    2,6-di-tert-butyl-4-dimethylaminomethylphenol; o-tert-butylphenol.-   2.2. Alkylated hydroquinones, for example    2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tert-butylhydroquinone;    2,5-di-tert-amylhydroquinone; 2,6-di-phenyl-4-octadecyloxyphenol.-   2.3. Hydroxylated thiodiphenyl ethers, for example    2,2′-thiobis(6-tert-butyl-4-methyl-phenol);    2,2′-thiobis(4-octylphenol);    4,4′-thiobis(6-tert-butyl-3-methylphenol);    4,4′-thiobis(6-tert-butyl-2-methylphenol).-   2.4. Alkylidenebisphenols, for example    2,2′-methylenebis(6-tert-butyl-4-methylphenol);    2,2′-methylenebis(6-tert-butyl-4-ethylphenol);    2,2′-methylenebis(4-methyl-6-(α-methylcyclohexyl)phenol);    2,2′-methylenebis(4-methyl-6-cyclohexylphenol);    2,2′-methylenebis(6-nonyl-4-methylphenol);    2,2′-methylenebis(4,6-di-tert-butylphenol);    2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol);    2,2′-methylenebis[6-□-methylbenzyl)-4-nonylphenol];    2,2′-methylenebis[6-(α, α-dimethylbenzyl)-4-nonylphenol];    4,4′-methylenebis(2,6-di-tert-butylphenol);    4,4′-methylenebis(6-tert-butyl-2-methylphenol);    1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;    2,6-di(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol;    1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane;    ethylene glycol    bis[3,3-bis(3′-tert-butyl-4′-hydroxylphenyl)butyrate];    di(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene;    di[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate.-   2.5. Benzyl compounds, for example    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene;    di(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide;    3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester;    bis(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl)dithioterephthalate;    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;    1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate;    3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester;    3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid mono-ethyl ester    calcium salt.-   2.6. Acylaminophenols, for example 4-hydroxylauric acid anilide;    4-hydroxystearic acid anilide;    2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyaniline)-s-triazine;    N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid octyl ester.-   2.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid    with mono- or polyhydric alcohols, e.g. with methanol; octadecanol;    1,6-hexanediol; neopentyl glycol; thiodiethylene glycol; diethylene    glycol; triethylene glycol; pentaerythritol;    tris(hydroxyethyl)isocyanurate; and di(hydroxyethyl)oxalic acid    diamide.-   2.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic    acid with mono- or polyhydric alcohols, e.g. with methanol;    octadecanol; 1,6-hexanediol; neopentyl glycol; thiodiethylene    glycol; diethylene glycol; triethylene glycol; pentaerythritol;    tris(hydroxyethyl)isocyanurate; and di(hydroxyethyl)oxalic acid    diamide.-   2.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,    e.g.,    N,N′-di(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)hexamethylenediamine;    N,N′-di(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine;    N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.-   3. Sulfurized organic compounds, for example aromatic, alkyl, or    alkenyl sulfides and polysulfines; sulfurized olefins; sulfurized    fatty acid esters; sulfurized ester olefins; sulfurized oils; esters    of β-thiodipropionic acid; sulfurized Diels-Alder adducts;    sulfurized terpene compounds; and mixtures thereof.-   4. Organo-borate compounds, for example alkyl- and aryl-(and mixed    alkyl, aryl) substituted borates.-   5. Phosphite and phosphate antioxidants, for example alkyl- and    aryl-(and mixed alkyl, aryl) substituted phosphites, and alkyl- and    aryl-(and mixed alkyl, aryl) substituted dithiophosphates such as    O,O,S-trialkyl dithiophosphates, O,O,S-triaryldithiophosphates and    dithiophosphates having mixed substitution by alkyl and aryl groups,    phosphorothionyl sulfide, phosphorus-containing silane,    polyphenylene sulfide, amine salts of phosphinic acid and quinone    phosphates.-   6. Copper compounds, for example copper dihydrocarbyl thio- or    dithiophosphates, copper salts of synthetic or natural carboxylic    acids, copper salts of alkenyl carboxylic acids or anhydrides such    as succinic acids or anhydrides, copper dithiocarbamates, copper    sulphonates, phenates, and acetylacetonates. The copper may be in    cuprous (Cu^(I)) or cupric (Cu^(II)) form.-   7. Zinc dithiodiphosphates, for example zinc    dialkyldithiophosphates, diphenyldialkyldithiophosphates, and    di(alkylphenyl)dithiophosphates.

In one embodiment, the compositions for use in the methods of thepresent invention, include but are not limited to:

a. a first antioxidant (in the concentration range, from about 0.0001%to about 50%, from about 0.0005% to about 20%, from about 0.005% toabout 10%, from about 0.05% to about 5% or from about 0.01% to about 1%)with a first additive selected from the group comprising a surfaceadditive, a performance enhancing additive and a lubricant performanceadditive, for example, in amounts of from about 0.0005% to about 50%,from about 0.0001% to about 20%, from about 0.005% to about 10%, fromabout 0.05% to about 5% or from about 0.01% to about 1% by weight, basedon the weight of lubricant to be stabilized.

b. the first antioxidant and the first additive as described in a. and asecond additive, for example, in concentrations of from about 0.0001% toabout 50% by weight, about 0.0005% to about 20% by weight, about 0.001%to about 10% by weight, from about 0.01% to about 5% by weight, fromabout 0.05% to about 1% by weight from about 0.1% to about 1% by weightbased on the overall weight of the lubricant to be stabilized.

c. the first antioxidant and the first additive as described in a. andoptionally the second additive as described in b. and a secondantioxidant, for example, Irganox® L 57, Irganox® 1010, Irganox® 1330,Irganox® 1076, Irganox® 5057 and Irganox® L 135 in the concentrationrange, from about 0.0001% to about 50%, from about 0.0005% to about 20%,from about 0.005% to about 10%, from about 0.05% to about 5% or fromabout 0.01% to about 1%) by weight, based on the weight of lubricant tobe stabilized.

In yet another embodiment, the antioxidant compositions for use in themethods of the present invention, includes but is not limited to: thefirst antioxidant from the present invention and the second antioxidantfrom the section ‘OTHER ANTIOXIDANTS AND STABILIZERS’. The antioxidantcomposition, where in the weight ratio of the second antioxidant to thefirst antioxidant of the present invention is from about 1:99 to 99:1,from about 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20,90:10. The second antioxidant second antioxidant, for example, Irganox®L 57, Irganox® L64, Irganox® 1330, Irganox® 1076, Irganox® 5057 andIrganox® L 135.

The term “alkyl” as used herein means a saturated straight-chain,branched or cyclic hydrocarbon. When straight-chained or branched, analkyl group is typically C1-C8, more typically C1-C6; when cyclic, analkyl group is typically C3-C12, more typically C3-C7 alkyl ester.Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl,n-butyl, sec-butyl and tert-butyl and 1, 1-dimethylhexyl.

The term “alkoxy” as used herein is represented by —OR**, wherein R** isan alkyl group as defined above.

The term “carbonyl” as used herein is represented by —C(═O)R**, whereinR** is an alkyl group as defined above.

The term “alkoxycarbonyl” as used herein is represented by —C(═O)OR**,wherein R** is an alkyl group as defined above.

The term “aromatic group” includes carbocyclic aromatic rings andheteroaryl rings. The term “aromatic group” may be used interchangeablywith the terms “aryl”, “aryl ring” “aromatic ring”, “aryl group” and“aromatic group”.

Carbocyclic aromatic ring groups have only carbon ring atoms (typicallysix to fourteen) and include monocyclic aromatic rings such as phenyland fused polycyclic aromatic ring systems in which a carbocyclicaromatic ring is fused to one or more aromatic rings (carbocyclicaromatic or heteroaromatic)r. Examples include 1-naphthyl, 2-naphthyl,1-anthracyl and 2-anthracyl. Also included within the scope of the term“carbocyclic aromatic ring”, as it is used herein, is a group in whichan aromatic ring is fused to one or more non-aromatic rings (carbocyclicor heterocyclic), such as in an indanyl, phthalimidyl, naphthimidyl,phenanthridinyl, or tetrahydronaphthyl, where the radical or point ofattachment is on the aromatic ring.

The term “heteroaryl”, “heteroaromatic”, “heteroaryl ring”, “heteroarylgroup” and “heteroaromatic group”, used alone or as part of a largermoiety as in “heteroaralkyl” refers to heteroaromatic ring groups havingfive to fourteen members, including monocyclic heteroaromatic rings andpolycyclic aromatic rings in which a monocyclic aromatic ring is fusedto one or more other aromatic ring (carbocyclic or heterocyclic).Heteroaryl groups have one or more ring heteroatoms. Examples ofheteroaryl groups include 2-furanyl, 3-furanyl, N-imidazolyl,2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl,5-isoxazolyl, oxadiazolyl, oxadiazolyl, 2-oxazolyl, 4-oxazolyl,5-oxazolyl, N-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl,N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl,2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl,4-pyridazinyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, triazolyl,tetrazolyl, 2-thienyl, 3-thienyl, carbazolyl, benzothienyl,benzofuranyl, indolyl, quinolinyl, benzothiazole, benzooxazole,benzimidazolyl, isoquinolinyl and isoindolyl. Also included within thescope of the term “heteroaryl”, as it is used herein, is a group inwhich an aromatic ring is fused to one or more non-aromatic rings(carbocyclic or heterocyclic), where the radical or point of attachmentis on the aromatic ring.

The term non-aromatic heterocyclic group used alone or as part of alarger moiety refers to non-aromatic heterocyclic ring groups havingthree to fourteen members, including monocyclic heterocyclcic rings andpolycyclic rings in which a monocyclic ring is fused to one or moreother non-aromatic carbocyclic or heterocyclic ring or aromatic ring(carbocyclic or heterocyclic). Heterocyclic groups have one or more ringheteroatoms, and can be saturated or unsaturated. Examples ofheterocyclic groups include piperidinyl, piperizinyl, pyrrolidinyl,pyrazolidinyl, imidazolidinyl, tetrahydroquinolinyl, inodolinyl,isoindolinyl, tetrahydrofuranyl, oxazolidinyl, thiazolidinyl,dioxolanyl, dithiolanyl, tetrahydropyranyl, dihydropyranyl, azepanyl andazetidinyl.

The term “heteroatom” means nitrogen, oxygen, or sulfur and includes anyoxidized form of nitrogen and sulfur, and the quaternized form of anybasic nitrogen. Also the term “nitrogen” includes substitutable nitrogenof a heteroaryl or non-aromatic heterocyclic group. As an example, in asaturated or partially unsaturated ring having 0-3 heteroatoms selectedfrom oxygen, sulfur or nitrogen, the nitrogen may be N (as in3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or NR″ (as inN-substituted pyrrolidinyl), wherein R″ is a suitable substituent forthe nitrogen atom in the ring of a non-aromatic nitrogen-containingheterocyclic group, as defined below.

As used herein the term non-aromatic carbocyclic ring as used alone oras part of a larger moiety refers to a non-aromatic carbon containingring which can be saturated or unsaturated having three to fourteenatoms including monocyclic and polycyclic rings in which the carbocyclicring can be fused to one or more non-aromatic carbocyclic orheterocyclic rings or one or more aromatic (carbocyclic or heterocyclic)rings.

An optionally substituted aryl group as defined herein may contain oneor more substitutable ring atoms, such as carbon or nitrogen ring atoms.Examples of suitable substituents on a substitutable ring carbon atom ofan aryl group include halogen (e.g., —Br, Cl, I and F), —OH, C1-C4alkyl, C1-C4 haloalkyl, —NO₂, C1-C4 alkoxy, C1-C4 haloalkoxy, —CN, —NH₂,C1-C4 alkylamino, C1-C4 dialkylamino, —C(O)NH₂, —C(O)NH(C1-C4 alkyl),—C(O)(C1-C4 alkyl), —OC(O)(C1-C4 alkyl), —OC(O)(aryl),—OC(O)(substituted aryl), —OC(O)(aralkyl), —OC(O)(substituted aralkyl),—NHC(O)H, —NHC(O)(C1-C4 alkyl), —C(O)N(C1-C4 alkyl)₂, —NHC(O)O—(C1-C4alkyl), —C(O)OH, —C(O)O—(C1-C4 alkyl), —NHC(O)NH₂, —NHC(O)NH(C1-C4alkyl), —NHC(O)N(C1-C4 alkyl)₂, —NH—C(═NH)NH₂,—SO₂NH₂—SO₂NH(C1-C3alkyl), —SO₂N(C1-C3alkyl)₂, NHSO₂H, NHSO₂(C1-C4alkyl) and optionally substituted aryl. Preferred substituents on arylgroups are as defined throughout the specification. In certainembodiments aryl groups are unsubstituted.

Examples of suitable substituents on a substitutable ring nitrogen atomof an aryl group include C1-C4 alkyl, NH₂, C1-C4 alkylamino, C1-C4dialkylamino, —C(O)NH₂, —C(O)NH(C1-C4 alkyl), —C(O)(C1-C4 alkyl), —CO₂R**, —C(O)C(O)R**, —C(O)CH₃, —C(O)OH, —C(O)O—(C1-C4 alkyl),—SO₂NH₂—SO₂NH(C1-C3alkyl), —SO₂N(C1-C3alkyl)₂, NHSO₂H, NHSO₂(C1-C4alkyl), —C(═S)NH₂, —C(═S)NH(C1-C4 alkyl), —C(═S)N(C1-C4 alkyl)₂,—C(═NH)—N(H)₂, —C(═NH)—NH(C1-C4 alkyl) and —C(═NH)—N(C1-C4 alkyl)₂,

An optionally substituted alkyl group or non-aromatic carbocyclic orheterocyclic group as defined herein may contain one or moresubstituents. Examples of suitable substituents for an alkyl groupinclude those listed above for a substitutable carbon of an aryl and thefollowing: ═O, ═S, ═NNHR**, ═NN(R**)₂, ═NNHC(O)R**, ═NNHCO₂ (alkyl),═NNHSO₂ (alkyl), ═NR**, spiro cycloalkyl group or fused cycloalkylgroup. R** in each occurrence, independently is —H or C1-C6 alkyl.Preferred substituents on alkyl groups are as defined throughout thespecification. In certain embodiments optionally substituted alkylgroups are unsubstituted.

A “spiro cycloalkyl” group is a cycloalkyl group which shares one ringcarbon atom with a carbon atom in an alkylene group or alkyl group,wherein the carbon atom being shared in the alkyl group is not aterminal carbon atom.

Without wishing to be bound by any theory or limited to any mechanism itis believed that macromolecular antioxidants and polymericmacromolecular antioxidants of the present invention exploit thedifferences in activities (ks, equilibrium constant) of, for example,homo- or hetero-type antioxidant moieties. Antioxidant moieties include,for example, hindered phenolic groups, unhindered phenolic groups,aminic groups and thioester groups, etc. of which there can be one ormore present in each macromolecular antioxidant molecule. As used hereina homo-type antioxidant macromolecule comprises antioxidant moietieswhich are all same, for example, hindered phenolic, —OH groups. As usedherein a hetero-type antioxidant macromolecule comprises at least onedifferent type of moiety, for example, hindered phenolic and aminicgroups in the one macromolecule.

This difference in activities can be the result of, for example, thesubstitutions on neighboring carbons or the local chemical or physicalenvironment (for example, due to electrochemical or stereochemicalfactors) which can be due in part to the macromolecular nature ofmolecules.

In one embodiment of the present invention, a series of macromolecularantioxidant moieties of the present invention with different chemicalstructures can be represented by W1H, W2H, W3H, . . . to WnH. In oneembodiment of the present invention, two types of antioxidant moietiesof the present invention can be represented by: W1H and W2H. In certainembodiments W1H and W2H can have rate constants of k1 and k2respectively. The reactions involving these moieties and peroxylradicals can be represented as:

where ROO. is a peroxyl radical resulting from, for example, initiationsteps involving oxidation activity, for example:RH→R.+H.  (3)R.+O2→ROO.  (4)

In one particular embodiment of the present invention k1>>k2 inequations (1) and (2). As a result, the reactions would take place insuch a way that there is a decrease in concentration of W1. freeradicals due their participation in the regeneration of active moietyW2H in the molecule according equation (5):W1.+W2H→W1H+W2.  (5) (transfer equilibrium)

This transfer mechanism may take place either in intra- orinter-molecular macromolecules. The transfer mechanism (5) could takeplace between moieties residing on the same macromolecule (intra-type)or residing on different macromolecules (inter-type).

In certain embodiments of the present invention, the antioxidantproperties described immediately above (equation 5) of themacromolecular antioxidants and polymeric macromolecular antioxidants ofthe present invention result in advantages including, but not limitedto:

-   -   a) Consumption of free radicals W1. according to equation (5)        can result in a decrease of reactions of W1. with hydroperoxides        and hydrocarbons (RH).    -   b) The regeneration of W1H provides extended protection of        materials. This is a generous benefit to sacrificial type of        antioxidants that are used today. Regeneration of W1H assists in        combating the oxidation process. The increase in the        concentration of antioxidant moieties W1H (according to        equation 5) extends the shelf life of materials.

In certain embodiments of the present invention, the following items areof significant interest for enhanced antioxidant activity in the designof the macromolecular antioxidants and polymeric macromolecularantioxidants of the present invention:

-   -   a) The activity of proposed macromolecular antioxidant is        dependent on the regeneration of W1H in equation (5) either        through inter- or intra-molecular activities involving homo- or        hetero-type antioxidant moieties.    -   b) Depending on the rates constants of W1H and W2H it is        possible to achieve performance enhancements by many multiples        and not just incremental improvements.

In certain embodiments of the present invention, more than two types ofantioxidant moieties with different rate constants are used in themethods of the present invention.

In certain embodiments, the present invention pertains to the use of thedisclosed compositions to improve materials, such as lubricants,lubricant oils, compositions comprising lubricants and lubricant oilsand mixtures thereof.

In certain embodiments, as defined herein improving a material meansinhibiting oxidation of an oxidizable material.

For purposes of the present invention, a method of “inhibitingoxidation” is a method that inhibits the propagation of a freeradical-mediated process. Free radicals can be generated by heat, light,ionizing radiation, metal ions and some proteins and enzymes. Inhibitingoxidation also includes inhibiting reactions caused by the presence ofoxygen, ozone or another compound capable of generating these gases orreactive equivalents of these gases.

As used herein the term “oxidizable material” is any material which issubject to oxidation by free-radicals or oxidative reaction caused bythe presence of oxygen, ozone or another compound capable of generatingthese gases or reactive equivalents thereof. In particular theoxidizable material is a lubricant or a mixture of lubricants.

In certain other embodiments, as defined herein improving a materialmeans inhibiting oxidation, as well as improving performance and/orincreasing the quality of a material, such as, a lubricant, lubricantoil, composition comprising a lubricant or lubricant oil or mixturesthereof. Increasing the quality of a material includes reducing frictionand wear, increasing viscosity, resistance to corrosion, aging orcontamination, etc. In certain embodiments, improving means that thelubricant is more resistant to degradation due to the presence ofoxygen, temperature, pressure, water, metal species and othercontributing factors to degradation. In certain embodiments, additive asdescribed herein help to promote the shelf life of these oils. Incertain embodiments the stability of the lubricants is directly relatedto their performance. That is the lubricant will not perform well if thelubricant has been degraded. In certain embodiments the performance ofthe lubricants is related to the additives. That is if antioxidant andadditives are used they will result in an improvement in the stabilityand performance of the lubricants.

A lubricant, as defined herein is a substance (usually a liquid)introduced between two moving surfaces to reduce the friction and wearbetween them. Lubricant can be used in, for example, automotive engines,and hydraulic fluids with transmission oils and the like. In addition toautomotive and industrial applications, lubricants are used for manyother purposes, including bio-medical applications (e.g. lubricants forartificial joints), grease, aviation lubricants, turbine enginelubricants, compressor oils, power transformer oils, automatictransmission fluids, metal working fluids, gear oils, sexual lubricantsand others.

In certain other embodiments of the present invention, lubricants arebiolubricants that are used as hydraulic fluid (bio hydraulic fluid),metal working fluid, gear oils (bio-gear oil), elevator oil, transformeroil, tractor oil, marine lubricants, grease, rock drill oil, chain sawbar oil, wire, rope and chain lubricants, stern tube lubricant,penetrating oils, aerosols, functional fluids, environmentallyacceptable lubricants (EALs), and many other industrial applications.Usually the base oil of biolubricant is bio-oil, synthetically modifiedbio-oil, biobased oil, and/or mixture of these bio-oils and biobasedoils with other Group I-V oils. Biolubricants are normallybiodegradable. Extent of biolubricants biodegradability is dependent onthe composition of base oil.

In certain other embodiments, as defined herein improving a materialmeans inhibiting oxidation, as well as improving performance and/orincreasing the quality of a material, such as polymers, copolymers andtheir blends, plastics, elastomers, polyolefins, thermoplasticelastomers, and nylons.

In one embodiment, of the present invention the compositions for use instabilization of polyolefins, include but are not limited to:

a. an antioxidant (in the concentration range, from about 0.0001% toabout 50%, from about 0.0005% to about 20%, from about 0.005% to about10%, from about 0.05% to about 5% or from about 0.01% to about 1%) withacid scavengers, for example, in amounts of from about 0.0005% to about50%, from about 0.0001% to about 20%, from about 0.005% to about 10%,from about 0.05% to about 5% or from about 0.01% to about 1% by weight,based on the weight of polyolefin to be stabilized.

b. an antioxidant (in the concentration range from about 0.0005% toabout 50%, from about 0.0001% to about 20%, from about 0.005% to about10%, from about 0.05% to about 5% or from about 0.01% to about 1%) alongwith organic phosphorus stabilizers. The organic phosphorus stabilizersare used for example, in amounts of, from about 0.001% to about 30%,from about 0.005% to about 20%, from about 0.01% to about 5%, from about0.05% to about 2% or from about 0.1% to about 1%, by weight, based onthe weight of the polyolefin to be stabilized.

c. an antioxidant (in the concentration range from about 0.0005% toabout 50%, from about 0.0001% to about 50%, from about 0.005% to about10%, from about 0.05% to about 5% or from about 0.01% to about 1%) alongwith acid scavengers and organic phosphorus stabilizers inconcentrations described in a. and b. above.

d. an antioxidant in combination with other known commercially availableantioxidants, such as, for example, Irganox® 1010, Irganox® 1330,Irganox® 1076 and Irganox® 1135 or other antioxidants described above orincorporated herein by reference along with the formulations describedin a.-c. above.

Polyolefins

In certain embodiments of the present invention, polyolefins andmixtures of polyolefins can be stabilized by contacting the polyolefinor mixture of polyolefins with a composition of the present invention.These polyolefins and mixtures of polyolefins, include, but are notlimited to substituted polyolefins, polyacrylates, polymethacrylates andcopolymers of polyolefins. The following are examples of some types ofpolyolefins which can be stabilized by the methods of the presentinvention:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityand high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), very low density polyethylene (VLDPE) and ultralow density polyethylene (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, for example polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   i) radical polymerization (normally under high pressure and at        elevated temperature).    -   ii) catalytic polymerization using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either p- or s-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium (III) chloride, and alumina or        silicon oxide. These catalysts may be soluble or insoluble in        the polymerization medium. The catalysts can be used by        themselves in the polymerization or further activators may be        used, typically metal alkyls, metal hydrides, metal alkyl        halides, metal alkyl oxides or metal alkyloxanes, said metals        being elements of groups Ia, IIa and/or IIIa of the Periodic        Table. The activators may be modified conveniently with further        ester, ether, amine or silyl ether groups. These catalyst        systems are usually termed Phillips, Standard Oil Indiana,        Ziegler (-Natta), TNZ (DuPont), metallocene or single site        catalysts (SSC).

2. Mixtures of the polymers mentioned under 1, for example, mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Blends of polymers mentioned under 1 with impact modifiers such asethylene-propylene-diene monomer copolymers (EPDM), copolymers ofethylene with higher alpha-olefins (such as ethylene-octene copolymers),polybutadiene, polyisoprene, styrene-butadiene copolymers, hydrogenatedstyrene-butadiene copolymers, styrene-isoprene copolymers, hydrogenatedstyrene-isoprene copolymers. These blends are commonly referred to inthe industry as TPO's (thermoplastic polyolefins).

In other embodiment polymers of the present invention includebiopolymers, bio copolymers, bio-elastomers, bioplastics and theirblends with synthetic polymers mentioned in sub-sections 1-4 of thepreceding paragraph.

In certain particular embodiments polyolefins of the present inventionare for example polypropylene homo- and copolymers and polyethylenehomo- and copolymers. For instance, some polyolefin Ares polypropylene,high density polyethylene (HDPE), linear low density polyethylene(LLDPE) and polypropylene random and impact (heterophasic) copolymers.

In certain particular embodiments polyolefins of the present inventionare for a wide range of industrial and house hold applications includingbut not limited to wire and cables, insulators and jackets, carriers andcontainers for solids, liquids and powders, packaging, automotive,aviation, and ship components and parts, industrial applications,papers, paints, tires, thin and thick sheets, solids, pipes and tubes,composites with other materials like for example carbon, wood, leather,and metals, electric, housing for wires, electric, electronic andoptical components including computers, filters and sponges,geo-membrane liners, housing and building components including roofingshingles, cosmetics, fragrance and toiletries, starch products, textileproducts and diapers.

Stabilizers

Acid Scavengers or Acid Stabilizers

“Acid scavengers or stabilizers” are defined herein as antacids orco-stabilizers which neutralize the acidic catalysts or other componentspresent in the polymers.

In certain embodiments, of the present invention the acid scavengerswhich are suitable for use in the methods of the present inventioninclude but are not limited to: zinc oxide, calcium lactate, natural andsynthetic hydrotalcites, natural and synthetic hydrocalumites, andalkali metal salts and alkaline earth metal salts of higher fatty acidsfor example calcium stearate, zinc stearate, magnesium behenate,magnesium stearate, sodium stearate, sodium ricinoleate and potassiumpalmitate, antimony pyrocatecholate and zinc pyrocatecholate.Combinations of acid scavengers may also be employed.

In certain particular embodiments, the acid scavengers are used forexample, in amounts of from about 0.0005% to about 50% by weight, about0.0001% to about 20% by weight, about 0.005% to about 5% by weight,about 0.01% to about 3% by weight, about 0.05% to about 2% by weight, orabout 0.1% to about 1% by weight, based on the weight of polyolefin tobe stabilized.

Organic Phosphorus Stabilizers

In certain embodiments of the present invention, examples of organicphosphorus stabilizers (or phosphorus stabilizers) include phosphates,phosphites and phosphonites which are suitable for use in the methods ofthe present invention. Specific examples of phosphorus stabilizersinclude but are not limited to: triphenyl phosphite, diphenyl alkylphosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite,trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritoldiphosphite, tris(2,4-di-tert-butylphenyl) phosphite, ethanamine,2-[[2,4,8,10-tetrakis(1,1dimethylethyl)dibenzo[d,f][1,2,3]dioxaphosphepin-6-yl]oxy]-N,N-[bis[2-[[2,4,8,10-tetrakis(1,1diemthylethyl)dibenzo[d,f][1,2,3]dioxaphepin-6-yl]oxy]ethyl](represented by structural formula (B) diisodecyl pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite(represented by structural formula (D) below),bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite(represented by structural formula (E) below),3,9-bis(octadecylpxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5undecane(represented by structural formula (F), bisisodecyloxy-pentaerythritoldiphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritoldiphosphite, bis¬(2,4,6-tri-tert-butylphenyl) pentaerythritoldiphosphite, tristearyl sorbitol triphosphite,tetrakis¬(2,4-di-tert-butylphenyl) 4,4′-biphenylene-diphosphonite(represented by structural formula (H) below),6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin(represented by structural formula (C) below),6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g][1,3,2]dioxaphosphocin(represented by structural formula (A) below),bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4di-tert-butyl-6-methylphenyl) ethyl phosphite (represented by structuralformula (G) below), (2,4,6-tri-tert-butylphenyl)2-butyl-2-ethyl-1,3-propanediol phosphate (represented by structuralformula (J) below), bis(2,4-di-cumylphenyl) pentaerythritol diphosphite(represented by structural formula (K) below), and structural formula(L) below:

In certain other embodiments of the present invention, the followingcompounds are examples of organic phosphites and phosphonites which aresuitable for use in the methods of the present invention as organicphosphorus stabilizers: tris(2,4-di-tert-butylphenyl) phosphite,bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (formula (D)),tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene-diphosphonite (formula(H)), (2,4,6-tri-tert-butylphenyl) 2-butyl-2-ethyl-1,3-propanediolphosphate (formula (J)), or bis(2,4-di-cumylphenyl) pentaerythritoldiphosphite (formula (K)).

The organic phosphorus stabilizers are used, for example, in amounts offrom about 0.001% to about 50% by weight, about 0.005% to about 20% byweight, about 0.01% to about 5% by weight, 0.05% to about 3% by weight,0.1% to about 2% by weight or 0.1% to about 1% by weight based on theweight of the polyolefin to be stabilized.

Co-Stabilizers

In certain embodiments of the present invention, in addition toantioxidants and stabilizers described above the compositions of thepresent invention may comprise further co-stabilizers (e.g., additives)such as, for example, the following:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-tert-butyl-4-octadecylphenol,2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,γ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for example dimethyl2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt ofthe monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard® XL-1, Crompton Corporation).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. Hindered Amine Stabilizers

As defined herein, “hindered amine stabilizers” are hindered amineswhich produce nitroxyl radicals that react with alkyl radicals producedduring thermo-oxidation of the polymers.

2.1. Sterically hindered amine stabilizers, for example4-hydroxy-2,2,6,6-tetramethylpiperidine,1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl) succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-piperidyl) succinate, linear orcyclic condensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-amino-propylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

The sterically hindered amine may also be one of the compounds describedin U.S. Pat. No. 5,980,783, the entire contents of which areincorporated herein by reference, that is compounds of component I-a),I-b), I-c), I-d), I-e), I-f), I-g), I-h), I-i), I-j), I-k) or I-l), inparticular the light stabilizer 1-a-1, 1-a-2, 1-b-1, 1-c-1, 1-c-2,1-d-1, 1-d-2, 1-d-3, 1-e-1, 1-f-1, 1-g-1, 1-g-2 or 1-k-1 listed oncolumns 64-72 of said U.S. Pat. No. 5,980,783.

The sterically hindered amine may also be one of the compounds describedin U.S. Pat. Nos. 6,046,304 and 6,297,299, the entire contents of eachof which are incorporated herein by reference.

2.2. Sterically hindered amines substituted on the N-atom by ahydroxy-substituted alkoxy group, for example compounds such as1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine,the reaction product of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidinewith a carbon radical from t-amylalcohol,1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidin-4-yl)sebacate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)succinate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarate and2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxy-ethylamino)-s-triazine.

3. Ultraviolet Absorbers

As defined herein “ultraviolet absorbers” essentially absorb the harmfulUV radiation and dissipate it so that is does not lead tophotosensitization i.e., dissipation as heat.

3.1. 2-(2-Hydroxyphenyl)-2H-benzotriazoles, for example known commercialhydroxyphenyl-2H-benzotriazoles and benzotriazoles as disclosed in, U.S.Pat. Nos. 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615;3,218,332; 3,230,194; 4,127,586; 4,226,763; 4,275,004; 4,278,589;4,315,848; 4,347,180; 4,383,863; 4,675,352; 4,681,905, 4,853,471;5,268,450; 5,278,314; 5,280,124; 5,319,091; 5,410,071; 5,436,349;5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987 and 5,977,219, theentire contents of each of which are incorporated herein by reference,such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,5-chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole,5-chloro-2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole,2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole,2-(3,5-di-tert-amyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-(co-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,phenyl)-2H-benzotriazole,2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole,dodecylated 2-(2-hydroxy-5-methylphenyl)-2-H-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole,2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole,2,2′-methylene-bis(4-tert-octyl-(6-2H-benzotriazol-2-yl)phenol),2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-tert-octyl-5-α-cumylphenyl)-2H-benzotriazole,5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzo-triazole,methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazoleand5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

3.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

3.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

3.4. Acrylates and malonates, for example, α-cyano-β,β-diphenylacrylicacid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methylester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butylester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline, Sanduvor® PR 25,(Clariant), dimethyl p-methoxybenzylidenemalonate (CAS #7443-25-6), andSanduvor® PR 31 (Clariant), di-(1,2,2,6,6-pentamethylpiperid-in-4-yl)p-methoxybenzylidenemalonate (CAS #147783-69-5).

3.5. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

3.6. Tris-aryl-o-hydroxyphenyl-s-triazines, for example known commercialtris-aryl-o-hydroxyphenyl-s-triazines and triazines as disclosed in, WO96/28431, EP 434608, EP 941989, GB 2,317,893, U.S. Pat. Nos. 3,843,371;4,619,956; 4,740,542; 5,096,489; 5,106,891; 5,298,067; 5,300,414;5,354,794; 5,461,151; 5,476,937; 5,489,503; 5,543,518; 5,556,973;5,597,854; 5,681,955; 5,726,309; 5,942,626; 5,959,008; 5,998,116 and6,013,704, the entire contents of each of which are incorporated hereinby reference, for example4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine(Cyasorb® 1164, Cytec Corp.),4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxpethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine,2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine,2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxy-propyloxy)phenyl]-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups),methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine},methylene bridged dimer mixture bridged in the 3:5′, 5:5′ and 3:3′positions in a 5:4:1 ratio,2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylsopropylideneoxy-phenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine,2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine,2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxapropyloxy)phenyl]-s-triazine,mixture of4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)-phenyl)-s-triazineand4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine,Tinuvin® 400, Ciba Specialty Chemicals Corp.,4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazineand 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.

4. Metal deactivators, as used herein are compounds which form stablecomplexes with metal ions and inhibit their reaction with peroxides, forexample, N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine,N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

5. Peroxide scavengers, for example, esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

6. Hydroxylamines, for example, N,N-dihydrocarbylhydroxylamines selectedfrom the group consisting of N,N-dibenzylhydroxylamine,N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine,N,N-bis(2-hydroxypropyl)hydroxylamine,N,N-bis(3-hydroxypropyl)-hydroxylamine,N,N-bis(2-carboxyethyl)hydroxylamine,N,N-bis(benzylthiomethyl)hydroxyl-amine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-didodecylhydroxylamine,N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine,N,N-dioctadecylhydroxylamine, N-hexadecyl-N-tetradecylhydroxylamine,N-hexadecyl-N-heptadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine,N-methyl-N-octadecylhydroxylamine, and N,N-di(hydrogenatedtallow)hydroxylamine.

The hydroxylamine may be for example the N,N-di(alkyl)hydroxylamineproduced by the direct oxidation of N,N-di(hydrogenated tallow)amine.For example, the hydroxylamine prepared by direct hydrogen peroxideoxidation of bis(hydrogenated tallow alkyl) amines that are N, N-di(hydrogenated tallow) hydroxylamine, CAS #143925-92-2.N,N-di(hydrogenated tallow)hydroxylamine is prepared as in the workingExamples of U.S. Pat. No. 5,013,510 the entire contents of which areincorporated herein by reference.

7. Nitrones, for example, N-benzyl-α-phenyl-nitrone,N-ethyl-α-methyl-nitrone, N-octyl-α-heptyl-nitrone,N-lauryl-α-undecyl-nitrone, N-tetradecyl-α-tridecyl-nitrone,N-hexadecyl-α-pentadecyl-nitrone, N-octadecyl-α-heptadecyl-nitrone,N-hexadecyl-α-heptadecyl-nitrone, N-ocatadecyl-α-pentadecyl-nitrone,N-heptadecyl-α-heptadecyl-nitrone, N-octadecyl-α-hexadecyl-nitrone,nitrone derived from N,N-di(hydrogenated tallow)hydroxylamine.

8. Amine-N-oxides, for example Genox™ EP, a di(C₁₆-C₁₈)alkyl methylamine oxide, CAS #204933-93-7, Crompton Corporation.

9. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. Nos. 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643;5,369,159; 5,488,117; 5,356,966; 5,367,008; 5,428,162; 5,428,177;5,516,920; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 orEP-A-0591102 the entire contents of each of which are incorporatedherein by reference, or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

10. Polyhydric alcohols, for example pentaerythritol and glycerol.

11. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides and polyurethanes.

12. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate, lithium benzoate, disodiumbicycle[2.2.1]heptane 2,3-dicarboxylate; organic phosphates and saltsthereof, e.g. sodium2,2′-methylenebis(4,6-di-tert-butylphenyl)phosphate, and polymericcompounds such as ionic copolymers (ionomers).

13. Clarifiers, for example substituted and unsubstituted bisbenzylidenesorbitols.

14. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, glass bulbs, asbestos, talc, wollastonite,nanoclays, kaolin, mica, barium sulfate, metal oxides and hydroxides,carbon black, graphite, wood flour and flours or fibers of other naturalproducts, synthetic fibers.

15. Dispersing Agents, as used herein are compounds which when added toa colloidal solution disperse the particles uniformly, such as, forexample, polyethylene oxide waxes or mineral oil.

16. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flame retardants, antistatic agents, antimicrobials andblowing agents.

In certain embodiments of the present invention the co-stabilizers areadded, for example, in concentrations of from about 0.0001% to about 50%by weight, about 0.0005% to about 20% by weight, about 0.001% to about10% by weight, from about 0.01% to about 5% by weight, from about 0.05%to about 1% by weight from about 0.1% to about 1% by weight based on theoverall weight of the polyolefin to be stabilized.

In certain other embodiments of the present invention the fillers andreinforcing agents, for example talc, calcium carbonate, mica or kaolin,are added to the polyolefins in concentrations of about 0.001% to about80% by weight, about 0.005% to about 60% by weight, about 0.01% to about40% by weight, of about 0.05% to about 20% by weight, of about 0.1% toabout 10% by weight, of about 0.5% to about 5% by weight, based on theoverall weight of the polyolefins to be stabilized.

In certain particular embodiments of the present invention the fillersand reinforcing agents, for example metal hydroxides, especiallyaluminum hydroxide or magnesium hydroxide, are added to the polyolefinsin concentrations of about 0.001% to about 80% by weight, about 0.005%to about 70% by weight, about 0.01% to about 60% by weight, about 0.1%to about 50% by weight about 0.5% to about 40% by weight about 1% toabout 20% by weight based on the overall weight of the polyolefins to bestabilized.

In certain particular embodiments of the present invention carbon blackas filler is added to the polyolefins in concentrations, judiciously, offrom about 0.001% to about 30% by weight, 0.005% to about 10% by weight,0.01% to about 5% by weight, of from about 0.05% to about 3% by weightof from about 0.1% to about 2% by weight of from about 0.1% to about 1%by weight based on the overall weight of the polyolefins to bestabilized.

In certain particular embodiments of the present invention glass fibersas reinforcing agents are added to the polyolefins in concentrations,judiciously, of from of about 0.001% to about 80% by weight, about0.005% to about 60% by weight, about 0.01% to about 40% by weight, ofabout 0.05% to about 20% by weight, of about 0.1% to about 10% byweight, based on the overall weight of the polyolefins to be stabilized.

The term “alkyl” as used herein means a saturated straight-chain,branched or cyclic hydrocarbon. When straight-chained or branched, analkyl group is typically C1-C8, more typically C1-C6; when cyclic, analkyl group is typically C3-C12, more typically C3-C7 alkyl ester.Examples of alkyl groups include methyl, ethyl, n propyl, iso propyl, nbutyl, sec butyl and tert butyl and 1,1-dimethylhexyl.

The term “alkoxy” as used herein is represented by —OR**, wherein R** isan alkyl group as defined above.

The term “acyl” as used herein is represented by —C(O)R**, wherein R**is an alkyl group as defined above.

The term “alkyl ester” as used herein means a group represented by—C(O)OR**, where R** is an alkyl group as defined above.

The term “aromatic group” used alone or as part of a larger moiety as in“aralkyl”, includes carbocyclic aromatic rings and heteroaryl rings. Theterm “aromatic group” may be used interchangeably with the terms “aryl”,“aryl ring” “aromatic ring”, “aryl group” and “aromatic group”.

Carbocyclic aromatic ring groups have only carbon ring atoms (typicallysix to fourteen) and include monocyclic aromatic rings such as phenyland fused polycyclic aromatic ring systems in which a carbocyclicaromatic ring is fused to one or more aromatic rings (carbocyclicaromatic or heteroaromatic). Examples include 1-naphthyl, 2-naphthyl,1-anthracyl and 2-anthracyl. Also included within the scope of the term“carbocyclic aromatic ring”, as it is used herein, is a group in whichan aromatic ring is fused to one or more non-aromatic rings (carbocyclicor heterocyclic), such as in an indanyl, phthalimidyl, naphthimidyl,phenanthridinyl, or tetrahydronaphthyl, where the radical or point ofattachment is on the aromatic ring.

The term “heteroaryl”, “heteroaromatic”, “heteroaryl ring”, “heteroarylgroup” and “heteroaromatic group”, used alone or as part of a largermoiety as in “heteroaralkyl” refers to heteroaromatic ring groups havingfive to fourteen members, including monocyclic heteroaromatic rings andpolycyclic aromatic rings in which a monocyclic aromatic ring is fusedto one or more other aromatic ring (carbocyclic aromatic orheteroaromatic). Heteroaryl groups have one or more ring heteroatoms.Examples of heteroaryl groups include 2-furanyl, 3-furanyl,N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl,4-isoxazolyl, 5-isoxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 2-oxazolyl,4-oxazolyl, 5-oxazolyl, 3-pyrazolyl, 4-pyrazolyl, 1-pyrrolyl,2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl,4-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl, 2-thiazolyl, 4-thiazolyl,5-thiazolyl, 2-triazolyl, 5-triazolyl, tetrazolyl, 2-thienyl, 3-thienyl,carbazolyl, 2 benzothienyl, 3 benzothienyl, 2 benzofuranyl, 3benzofuranyl, 2 indolyl, 3 indolyl, 2 quinolinyl, 3 quinolinyl, 2benzothiazole, 2 benzooxazole, 2 benzimidazolyl, 2 quinolinyl, 3quinolinyl, 1 isoquinolinyl, 3 quinolinyl, 1 isoindolyl and 3isoindolyl. Also included within the scope of the term “heteroaryl”, asit is used herein, is a group in which an aromatic ring is fused to oneor more non-aromatic rings (carbocyclic or heterocyclic), where theradical or point of attachment is on the aromatic ring.

The term “heteroatom” means nitrogen, oxygen, or sulfur and includes anyoxidized form of nitrogen and sulfur, and the quaternized form of anybasic nitrogen. Also the term “nitrogen” includes substitutable nitrogenof a heteroaryl or non-aromatic heterocyclic group. As an example, in asaturated or partially unsaturated ring having 0-3 heteroatoms selectedfrom oxygen, sulfur or nitrogen, the nitrogen may be N (as in3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or NR″ (as inN-substituted pyrrolidinyl), wherein R″ is a suitable substituent forthe nitrogen atom in the ring of a non-aromatic nitrogen-containingheterocyclic group, as defined below.

An “aralkyl group”, as used herein is an alkyl groups substituted withan aryl group as defined above.

An optionally substituted aryl group as defined herein may contain oneor more substitutable ring atoms, such as carbon or nitrogen ring atoms.Examples of suitable substituents on a substitutable ring carbon atom ofan aryl group include —OH, C1-C3 alkyl, C1-C3 haloalkyl, —NO₂, C1-C3alkoxy, C1-C3 haloalkoxy, —CN, —NH₂, C1-C3 alkylamino, C1-C3dialkylamino, —C(O)NH₂, —C(O)NH(C1-C3 alkyl), —C(O)(C1-C3 alkyl),—NHC(O)H, —NHC(O)(C1-C3 alkyl), —C(O)N(C1-C3 alkyl)₂, —NHC(O)O—(C1-C3alkyl), —C(O)OH, —C(O)O—(C1-C3 alkyl), —NHC(O)NH₂, —NHC(O)NH(C1-C3alkyl), —NHC(O)N(C1-C3 alkyl)₂, —SO₂NH₂—SO₂NH(C1-C3alkyl),—SO₂N(C1-C3alkyl)₂, NHSO₂H or NHSO₂(C1-C3 alkyl). Preferred substituentson aryl groups are as defined throughout the specification. In certainembodiments optionally substituted aryl groups are unsubstituted.

Examples of suitable substituents on a substitutable ring nitrogen atomof an aryl group include C1-C3 alkyl, NH₂, C1-C3 alkylamino, C1-C3dialkylamino, —C(O)NH₂, —C(O)NH(C1-C3 alkyl), —C(O)(C1-C3 alkyl), —CO₂R**, —C(O)C(O)R**, —C(O)CH₃, —C(O)OH, —C(O)O—(C1-C3 alkyl),—SO₂NH₂—SO₂NH(C1-C3alkyl), —SO₂N(C1-C3alkyl)₂, NHSO₂H, NHSO₂(C1-C3alkyl), —C(═S)NH₂, —C(═S)NH(C1-C3 alkyl), —C(═S)N(C1-C3 alkyl)₂,—C(═NH)—N(H)₂, —C(═NH)—NH(C1-C3 alkyl) and —C(═NH)—N(C1-C3 alkyl)₂.

An optionally substituted alkyl group as defined herein may contain oneor more substituents. Examples of suitable substituents for an alkylgroup include those listed above for a substitutable carbon of an aryland the following: ═O, ═S, ═NNHR**, ═NN(R**)₂, ═NNHC(O) R**, ═NNHCO₂(alkyl), ═NNHSO₂ (alkyl), ═NR**, spiro cycloalkyl group or fusedcycloalkyl group. R** in each occurrence, independently is —H or C1-C6alkyl. Preferred substituents on alkyl groups are as defined throughoutthe specification. In certain embodiments optionally substituted alkylgroups are unsubstituted.

A “spiro cycloalkyl” group is a cycloalkyl group which shares one ringcarbon atom with a carbon atom in an alkylene group or alkyl group,wherein the carbon atom being shared in the alkyl group is not aterminal carbon atom.

The polyamide is generally known as nylon having the formula—NH—(CH₂)_(x)—CO—

where x is an integer, preferably 6, 9, 10, 11 or 12. Any suitable nylonmay be employed as the base resin in the composition according to theinvention. Preferred nylons are Nylon-6 (polycaprolactam), Nylon-6,6(polyhexamethylene adipamide), Nylon-6,9 (polyhexamethylene azelaamide),Nylon-6,10 (polyhexamethylene sebacamide), Nylon-6,12(polyhexamethylenedodecanoamide), Nylon-1(polyundecanoamide) and Nylon-12(polydodecanoamide). The nylon base resin will be preferably 100% of theunits represented by the formula, but it may also contain non-polyamideunits, e.g. an olefin homopolymer or copolymer. In suchpolycopolyamides, polyamides generally comprise at least 25%, preferablyat least 75%, particularly essentially 100% units having the aboveformula.

In another embodiment the polymer is selected from the group consistingof polyamide, polyester and combination thereof, preferably polymer isselected from the group consisting of polyamide, such as nylon 6, nylon66, nylon 10, nylon1010, nylon 12, nylon1212, nylon610, nylon 612, PPA,PA6T, PA9T and combination thereof, and preferably the polymer isselected from the group consisting of PET, PBT, PTT and combinationsthereof.

As disclosed in Kirk-Othmer Encyclopedia of Chemical Technology, Volume19, pages 772-797, polyamide composition which is incorporated herein byreference, nylon may be compounded with a wide range of additives thatinclude lubricants to improve the melt flow, screw feeding and moldrelease; nucleants which are finely dispersed seed the molten nylon andresult in a higher density of small uniformly sized spherulites toincrease the tensile strength and stiffness; stabilizers to slow downthe rate of oxidation and UV aging by adding antioxidants, ultravioletstabilizers, hydro-peroxide decomposers, or metal salts mostly in theform of copper halide mixtures; impact modifiers to improve the notchedimpact strength and ductility by adding rubbers, olefin copolymerssilicones, polyurethanes or modified acrylics; flame retardants to aidinhibiting the combustion process and eliminating burning drips byadding halogenated organics; plastisizers to increase the flexibility ofnylon and to improve the impact strength, and reinforcement by addingsuch as glass fibers or nylon mixing with nanometer size silicates tomake nanocomposites to improve the tensile strength and stiffness. Tobalance the properties nylon are sometimes blended with other polymerse.g. polyethylene or polypropylene.

Description of Polyamides:

Examples of thermoplastic polyamides useful in the compositions of thepresent invention include semicrystalline or amorphous aliphatic andsemi-aromatic polyamides as well as mixtures thereof.

Suitable aliphatic polyamides are derived from aliphatic lactams oraliphatic diamines and dicarboxylic acids and include, for example,polyamide 6, polyamide 11, polyamide 12, polyamide 6,6, polyamide 4,6,polyamide 6,10, polyamide 6,12. Suitable aliphatic polyamides alsoinclude copolyamides derived from mixtures of aliphatic diamines,aliphatic dicarboxylic acids, and aliphatic lactams.

Suitable semi-aromatic polyamides are derived from at least one aromaticdiamine and/or aromatic dicarboxylic acid monomer and other aliphaticmonomers, which may include aliphatic diamines, aliphatic dicarboxylicacids, and aliphatic lactams. Specific examples include PA-6, I, PA-6,I/6,6-copolyamide, PA-6, T, PA-6, T/6-copolyamide, PA-6,T/6,6-copolyamide, PA-6, I/6, T-copolyamide, PA-6,6/6,T/6,1-copolyamide, PA-6, T/2-MPMD, T-copolyamide(2-MPMD=2-methylpentamethylene diamine), PA-9, T, and PA-9T/2-MOMD, T(2-MOMD=2-methyl-1,8-octamethylenediamine).

Description of Stabilizers for Polyamides:

Heat stabilizing systems for polyamides typically comprise one or moreadditives selected from the groups of phenolic antioxidants, low-valentphosphorus compounds, aromatic amines, copper salts alone or incombination with one or more alkali or alkaline earth metal halide saltsmetal salts, and the transition metals and their oxides.

Phenolic antioxidants suitable for use in polyamides are well known inthe art and are described by K. Schwarzenbach et al. in “PlasticAdditives Handbook”, 5^(th) ed., H. Zweifel, Ed., Hanser Publishers,Chapter 1, which is incorporated herein in its entirety by reference.Examples of preferred phenolic antioxidants for use in polyamidesinclude:

-   -   N,N′-Hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide],        Chemical Abstract Service Registry No. 23128-74-7, available        from BASF as Irganox® 1098,    -   [1,2-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoyl]hydrazine,        Chemical Abstract Service Registry No. 32687-87-8, available        from BASF as Irganox® MD 1024,    -   Pentaerythritol        tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],        Chemical Abstract Service Registry No. 6683-19-8, available from        BASF as Irganox® 1010,    -   1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,        Chemical Abstract Service Registry No. 1709-70-2, available from        Albemarle Corporation as Ethanox® 330,    -   Butylated reaction product of p-cresol and dicyclopentadiene,        Chemical Abstract Service Registry No. 68610-51-5, available        from ELIOKEM as Wingstay® L,    -   N-(4-hydroxyphenyl)octadecanamide, Chemical Abstract Service        Registry No. 103-99-1,    -   2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methyl)        benzyl-4-methylphenyl acrylate, Chemical Abstract Service        Registry No. 61167-58-6, available from Sumitomo as Sumilizer®        GM,    -   2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,        6-di-tert-pentylphenyl acrylate, Chemical Abstract Service        Registry No. 123968-25-2, available from Sumitomo as Sumilizer®        GS, and    -   2,6-Di-tert-butyl-4-[4,6-bis(octylthio)-1,3,5-triazin-2-ylamino]phenol,        Chemical Abstract Service Registry No. 991-84-4, available from        BASF as Irganox® 565.

Low-valent phosphorus compounds suitable for use in polyamides includeorganic phosphites and phosphonites, salts of phenylphosphinic acid, andhypophosphite salts. Organic phosphites and phosphonites suitable foruse in polyamides are well known in the art and are described by K.Schwarzenbach et al. in “Plastic Additives Handbook”, 5^(th) ed., H.Zweifel, Ed., Hanser Publishers, Chapter 1, which is incorporated hereinin its entirety by reference. Examples of preferred organic phosphitesand phosphonites for use in polyamides include:

-   -   Tris(2,4-di-tert-butylphenyl)phosphite, Chemical Abstract        Service Registry No. 31570-04-4, available from BASF as Irgafos®        168,    -   Bis(2,4-dicumylphenyl) pentaerythritol diphosphite, Chemical        Abstract Service Registry No. 154862-43-8, available from Dover        Chemical as Doverphos® S-9228,    -   Bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol        diphosphite, available from Amfine Chemical as ADK Stab® PEP-36,        and    -   Tetrakis(2,4-di-tert-butylphenyl)[1,1′-biphenyl]4,4′-diylbisphosphonite,        Chemical Abstract Service Registry No. 119345-01-6, available        from Clariant as Hostanox® P-EPQ.

Examples of salts of phenylphosphinic acid suitable for use inpolyamides include sodium phenylphosphinate (Chemical Abstract ServiceRegistry No. 4297-95-4), zinc phenylphosphinate (Chemical AbstractService Registry No. 25070-22-8), and other phenylphosphinate salts ofalkali metals and alkaline earth metals.

Examples of hypophosphite salts include sodium hypophosphite (ChemicalAbstract Service Registry No. 7681-53-0), sodium hypophosphitemonohydrate (Chemical Abstract Service Registry No. 10039-56-2) andother hypophosphite salts of alkali metals and alkaline earth metals andtheir hydrates.

Aromatic amine antioxidants suitable for use in polyamides are wellknown in the art and are described by K. Schwarzenbach et al. in“Plastic Additives Handbook”, 5^(th) ed., H. Zweifel, Ed., HanserPublishers, Chapter 1, which is incorporated herein in its entirety byreference. Examples of preferred aromatic amine antioxidants for use inpolyamides include:

-   -   4,4′-Bis(α, α-dimethylbenzyl)diphenylamine, Chemical Abstract        Service Registry No. 10081-67-1, available from Chemtura as        Naugard® 445,    -   Acetone-diphenylamine condensation product, Chemical Abstract        Service Registry No. 9003-79-6, available from Chemtura as        Naugard® A, and    -   Styrenated diphenylamines, Chemical Abstract Service Registry        No. 68442-68-2, available from ELIOKEM as Wingstay® 29.

Examples of suitable copper salts include copper (I) and copper (II)salts, for example, copper phosphates, copper halides, and copperacetates. Suitable alkali metal halides for use in combination with thecopper salts include the chlorides, bromides and iodides of lithium,sodium, potassium, and cesium. Examples of suitable alkaline earth metalhalides for use in combination with the copper salts include thechlorides, bromides, and iodides of calcium. Suitable copper (I)halide/alkali metal halide combinations include, for example, CuI/KI andCuI/KBr. When used in combination, preferred ratios of the copper saltto the alkali metal or alkaline earth salt range from about 1:50 toabout 2:1 by weight.

Examples of suitable transition metals and their oxides include iron,copper, and the iron oxides.

The preferred concentration of component of the heat stabilizing systemranges from about 0.05% to about 10% by weight, from about 0.01% toabout 5%, from about 0.01% to about 3%, from about 0.01% to about 1%,based on the weight of thermoplastic polyamide polymer being stabilized.

In one embodiment, of the present invention the compositions for use instabilization of polyamides, copolyamides, polyesters, copolyesters andblend of polymer or copolymer with one or more other polymers includebut are not limited to:

a. an antioxidant of the instant invention (in the concentration range,from about 0.0001% to about 50%, from about 0.0005% to about 20%, fromabout 0.005% to about 10%, from about 0.05% to about 5% or from about0.01% to about 1%) with acid scavengers, for example, in amounts of fromabout 0.0005% to about 50%, from about 0.0001% to about 20%, from about0.005% to about 10%, from about 0.05% to about 5% or from about 0.01% toabout 1% by weight, based on the weight of polymer or copolymer or blendof polymer with the other polymers or copolymers and blend of polymer orcopolymer with one or more other polymers to be stabilized.

b. an antioxidant of the instant invention (in the concentration rangefrom about 0.0005% to about 50%, from about 0.0001% to about 20%, fromabout 0.005% to about 10%, from about 0.05% to about 5% or from about0.01% to about 1%) along with organic phosphorus stabilizers. Theorganic phosphorus stabilizers are used for example, in amounts of, fromabout 0.001% to about 30%, from about 0.005% to about 20%, from about0.01% to about 5%, from about 0.05% to about 2% or from about 0.1% toabout 1%, by weight, based on the weight of the polymer to bestabilized.

c. an antioxidant of the instant invention (in the concentration rangefrom about 0.0005% to about 50%, from about 0.0001% to about 50%, fromabout 0.005% to about 10%, from about 0.05% to about 5% or from about0.01% to about 1%) along with low valent phosphorus compounds, aromaticamine antioxidants, copper salts alone or in combination with one ormore alkali or alkaline earth metal halide salts, and transition metalsand their oxides in a. and b. above. These additives are used forexample, in amounts of, from about 0.001% to about 30%, from about0.005% to about 20%, from about 0.01% to about 5%, from about 0.05% toabout 2% or from about 0.1% to about 1%, by weight, based on the weightof the polymer to be stabilized.

d. an antioxidant of the instant invention (in the concentration rangefrom about 0.0005% to about 50%, from about 0.0001% to about 50%, fromabout 0.005% to about 10%, from about 0.05% to about 5% or from about0.01% to about 1%) along with polyfunctional epoxides, polyhydricalcohols, and polyfunctional carboxylic acids and anhydrides. Theseadditives are used for example, in amounts of, from about 0.001% toabout 30%, from about 0.005% to about 20%, from about 0.01% to about 5%,from about 0.05% to about 2% or from about 0.1% to about 1%, by weight,based on the weight of the polymer to be stabilized.

e. an antioxidant of the instant invention in combination with otherknown commercially available antioxidants, such as, for example, 1010,Irganox® 1330, Irganox® 1076, Irganox® 1135, aromatic aminesantioxidants Naugard 445, Naugard A, Winstay 29 or other antioxidantsdescribed above or incorporated herein by reference along with theformulations described in a.-d. above.

EXEMPLIFICATION Example 1: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,4-dimethyl-pentyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride

In a one liter of 3-neck round bottom flask, 25.0 g ofN-(1,4-Dimethyl-pentyl)-N′-phenyl-benzene-1,4-diamine was dissolved in200 ml of anhydrous toluene under argon atmosphere. 25 ml of triethylamine was added drop wise. 30 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride was dissolvedin 200 ml of anhydrous toluene and was transferred drop wise to theround bottom flask containingN-(1,4-Dimethyl-pentyl)-N′-phenyl-benzene-1,4-diamine under argonatmosphere. Reactants were heated to reflux temperature of toluene (111°C.). The reaction was completed in 6 hours. The crude product thusobtained was purified by washing with cold hexane to get 29.5 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,4-dimethyl-pentyl)-N-(4-phenylamino-phenyl)-propionamideand the structure was confirmed by 500 MHz H NMR spectroscopy withresonance peaks at 0.9-1.1 (m), 1.33 (m), 1.41 (s), 1.61 (m), 1.91 (m),2.3 (t), 2.85 (t), 3.88 (m), 6.81 (m), 6.86 (s), 7.01 (m), 7.13-7.15(m), 7.32-7.35 (m) ppm.

Example 2: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride

In a 100 ml of 3-neck round bottom flask, 1.0 g ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine was dissolved in 20ml of anhydrous toluene under argon atmosphere. 0.75 ml of triethylamine was added drop wise. 1.4 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride was dissolvedin 20 ml of anhydrous toluene and was transferred drop wise to the roundbottom flask containingN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine under argonatmosphere. Reactants were heated to reflux temperature of toluene (111°C.). The reaction was completed in 5 hours. The crude product thusobtained was purified by washing with cold hexane to get 1.5 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamideand the structure was confirmed by 500 MHz H NMR with peaks appearing at0.9-1.1 (m), 1.42 (s), 1.61 (m), 1.94 (m), 2.28 (t), 2.83 (t), 3.89 (m),6.83 (m), 6.88 (s), 7.03 (m), 7.13-7.15 (m), 7.32-7.35 (m) ppm.

Example 3: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-isopropyl-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride

In a 100 ml of 3-neck round bottom flask, 1.0 g ofN-Isopropyl-N′-phenyl-benzene-1,4-diamine is dissolved in 20 ml ofanhydrous toluene under argon atmosphere. 0.75 ml of triethyl amine isadded drop wise. 1.3 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride is dissolvedin 20 ml of anhydrous toluene and is transferred drop wise to the roundbottom flask containing N-Isopropyl-N′-phenyl-benzene-1,4-diamine.Reactants are heated to reflux temperature of toluene (111° C.). Thereaction is completed in 5 hours. The crude product thus obtained ispurified by washing with cold hexane to get 1.4 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-isopropyl-N-(4-phenylamino-phenyl)-propionamide.

Example 4: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride

In a 100 ml of 3-neck round bottom flask, 1.0 g ofN-Phenyl-benzene-1,4-diamine is dissolved in 20 ml of anhydrous tolueneunder argon atmosphere. 0.75 ml of triethyl amine is added drop wise.1.2 g of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride isdissolved in 20 ml of anhydrous toluene and is transferred drop wise tothe round bottom flask containing N-Phenyl-benzene-1,4-diamine.Reactants are heated to reflux temperature of toluene (111° C.). Thereaction is completed in 4 hours. The crude product thus obtained ispurified by washing with cold hexane to get 1.2 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 5: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,4-dimethyl-pentyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid

In a set-up of Dean-Stark apparatus, 1.0 g ofN-(1,4-Dimethyl-pentyl)-N′-phenyl-benzene-1,4-diamine is dissolved in 40ml of anhydrous toluene. 1.4 g of 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid and a catalytic amount of boric acid (0.024 g) are addedto the flask. The reaction mixture is refluxed under argon atmospherefor 15 hours. The crude product thus obtained is purified to get3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,4-dimethyl-pentyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 6: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid

In a set-up of Dean-Stark apparatus, 1.0 g ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine is dissolved in 40ml of anhydrous toluene. 1.3 g of 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid and a catalytic amount of boric acid (0.024 g) are addedto the flask. The reaction mixture is refluxed under argon atmospherefor 15 hours. The crude product thus obtained is purified to get3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 7: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-isopropyl-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid

In a set-up of Dean-Stark apparatus, 1.0 g ofN-Isopropyl-N′-phenyl-benzene-1,4-diamine is dissolved in 40 ml ofanhydrous toluene. 1.3 g of 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid and a catalytic amount of boric acid (0.024 g) are addedto the flask. The reaction mixture is refluxed under argon atmospherefor 15 hours. The crude product thus obtained is purified to get3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-isopropyl-N-(4-phenylamino-phenyl)-propionamide.

Example 8: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid

In a set-up of Dean-Stark apparatus, 1.0 g ofN-Phenyl-benzene-1,4-diamine is dissolved in 40 ml of anhydrous toluene.1.3 g of 3-(3,5-ditert-butyl-4-hydroxyphenyl) propanoic acid and acatalytic amount of boric acid (0.024 g) are added to the flask. Thereaction mixture is refluxed under argon atmosphere for 15 hours. Thecrude product thus obtained is purified to get3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 9: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,4-dimethyl-pentyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester

In a set-up of Dean-Stark apparatus, 1.0 g ofN-(1,4-Dimethyl-pentyl)-N′-phenyl-benzene-1,4-diamine is dissolved in 40ml of anhydrous toluene. 1.4 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester and acatalytic amount of boric acid (0.024 g) are added to the flask. 10 g of4 A° molecular sieves are added in the dean stark to absorb theeliminated methanol during the course of reaction. The reaction mixtureis refluxed under argon atmosphere for 15 hours. The crude product thusobtained is purified to get3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,4-dimethyl-pentyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 10: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester

In a set-up of Dean-Stark apparatus, 1.0 g ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine is dissolved in 40ml of anhydrous toluene. 1.3 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester and acatalytic amount of boric acid (0.024 g) are added to the flask. 10 g of4 A° molecular sieves are added in the dean stark to absorb theeliminated methanol during the course of reaction. The reaction mixtureis refluxed under argon atmosphere for 15 hours. The crude product thusobtained is purified to get3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 11: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-isopropyl-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester

In a set-up of Dean-Stark apparatus, 1.0 g ofN-Isopropyl-N′-phenyl-benzene-1,4-diamine is dissolved in 40 ml ofanhydrous toluene. 1.3 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester and acatalytic amount of boric acid (0.024 g) are added to the flask. 10 g of4 A° molecular sieves are added in the dean stark to absorb theeliminated methanol during the course of reaction. The reaction mixtureis refluxed under argon atmosphere for 15 hours. The crude product thusobtained is purified to get3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-isopropyl-N-(4-phenylamino-phenyl)-propionamide.

Example 12: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester

In a set-up of Dean-Stark apparatus, 1.0 g ofN-Phenyl-benzene-1,4-diamine is dissolved in 40 ml of anhydrous toluene.1.3 g of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methylester and a catalytic amount of boric acid (0.024 g) are added to theflask. 10 g of 4 A° molecular sieves are added in the dean stark toabsorb the eliminated methanol during the course of reaction. Thereaction mixture is refluxed under argon atmosphere for 15 hours. Thecrude product thus obtained is purified to get3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 13: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1-methyl-heptyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride

In a 100 ml of 3-neck round bottom flask, 1.0 g ofN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine was dissolved in 20 mlof anhydrous toluene under argon atmosphere. 0.75 ml of triethyl aminewas added drop wise. 1.4 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride was dissolvedin 20 ml of anhydrous toluene and was transferred drop wise to the roundbottom flask containingN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine under argonatmosphere. Reactants were heated to reflux temperature of toluene (111°C.). The reaction was completed in 5 hours. The crude product thusobtained was purified by washing with cold hexane to get 1.5 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1-methyl-heptyl)-N-(4-phenylamino-phenyl)-propionamide.The structure was confirmed by 500 MHz ¹H NMR with peaks appearing at0.91 (m), 1.3-1.41 (m), 1.44 (s), 1.61 (m), 2.3 (t), 2.85 (t), 3.88 (m),6.81 (m), 6.86 (s), 7.01 (m), 7.13-7.15 (m), 7.32-7.35 (m) ppm.

Example 14: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1-methyl-heptyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid

In a set-up of Dean-Stark apparatus, 1.0 g ofN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine is dissolved in 40 mlof anhydrous toluene. 1.3 g of 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid and a catalytic amount of boric acid (0.024 g) are addedto the flask. The reaction mixture is refluxed under argon atmospherefor 15 hours. The crude product thus obtained is purified to get3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1-methyl-heptyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 15: Synthesis of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1-methyl-heptyl)-N-(4-phenylamino-phenyl)-propionamideUsing 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester

In a set-up of Dean-Stark apparatus, 1.0 g ofN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine is dissolved in 40 mlof anhydrous toluene. 1.3 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester and acatalytic amount of boric acid (0.024 g) are added to the flask. 10 g of4 A° molecular sieves are added in the dean stark to absorb theeliminated methanol during the course of reaction. The reaction mixtureis refluxed under argon atmosphere for 15 hours. The crude product thusobtained is purified to get3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1-methyl-heptyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 16: Reaction Product of Synthesis of Mixture ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine andN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine Using3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionyl chloride

In a 100 ml of 3-neck round bottom flask, 0.5 g ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine and 0.5 g ofN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine were dissolved in 20ml of anhydrous toluene under argon atmosphere. 0.8 ml of triethyl aminewas added. 1.5 g of 3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionylchloride was dissolved in 20 ml of anhydrous toluene and was transferreddrop wise to the round bottom flask containingN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine andN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine under argonatmosphere. Reactants were heated to reflux temperature of toluene (111°C.). The reaction was completed in 1 hour. The crude product thusobtained was purified by washing with cold hexane to get 1.4 g ofreaction product of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamideand3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1-methyl-heptyl)-N-(4-phenylamino-phenyl)-propionamide.The structure was confirmed by 500 MHz H NMR with peaks appearing at0.9-1.1 (m), 1.3-1.41 (m), 1.44 (s), 1.61 (m), 1.94 (m), 2.3 (t), 2.85(t), 3.88 (m), 6.81 (m), 6.86 (s), 7.01 (m), 7.13-7.15 (m), 7.32-7.35(m) ppm.

Example 17: Reaction Product of Synthesis of Mixture ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine andN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine Using3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid

In a set-up of Dean-Stark apparatus, 0.5 g ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine and 0.5 g ofN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine are dissolved in 40 mlof anhydrous toluene. 1.4 g of 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid and a catalytic amount of boric acid (0.024 g) are addedto the flask. The reaction mixture is refluxed under argon atmospherefor 15 hours. The crude product thus obtained is purified to getreaction product of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamideand3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1-methyl-heptyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 18: Reaction Product of Synthesis of Mixture ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine andN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine Using3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester

In a set-up of Dean-Stark apparatus, 0.5 g ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine and 0.5 g ofN-(1-Methyl-heptyl)-N′-phenyl-benzene-1,4-diamine are dissolved in 40 mlof anhydrous toluene. 1.3 g of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-propionic acid methyl ester and acatalytic amount of boric acid (0.024 g) are added to the flask. 10 g of4 A° molecular sieves are added in the dean stark to absorb theeliminated methanol during the course of reaction. The reaction mixtureis refluxed under argon atmosphere for 15 hours. The crude product thusobtained is purified to get reaction product of3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1,3-dimethyl-butyl)-N-(4-phenylamino-phenyl)-propionamideand3-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-N-(1-methyl-heptyl)-N-(4-phenylamino-phenyl)-propionamide.

Example 19: Synthesis of4-[3-{4,6-Bis-[(1,3-dimethyl-butyl)-(4-phenylamino-phenyl)-amino]-[ ],3,5]triazin-2-yloxy}-propyl)-2, 6-di-tert-butyl-phenol Using 2,4,6-Trichloro-[1, 3,5]triazine

In a 100 ml of 3-neck round bottom flask, 1.0 g of2,4,6-Trichloro-[1,3,5]triazine was dissolved in 25 ml of anhydroustetrahydrofuran under nitrogen atmosphere. 3.1 ml of triethyl amine wasadded. 4.45 g of N-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diaminewas transferred to the round bottom flask under nitrogen atmosphere.Reactants were heated to reflux temperature of tetrahydrofuran (65° C.).The reaction was completed in 20 hours. The crude product thus obtainedwas purified to get 4.1 g of4-(3-{4,6-Bis-[(1,3-dimethyl-butyl)-(4-phenylamino-phenyl)-amino]-[1,3,5]triazin-2-yloxy}-propyl)-2,6-di-tert-butyl-phenol.The structure was confirmed by 500 MHz H NMR with peaks appearing at1.34 (s), 2.54 (t), 2.64 (t), 6.72 (s), 6.77 (d), 6.81 (s), 6.98 (d)ppm.

Example 20: Synthesis of4-[3-({4,6-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propoxy]-1,3,5-triazin-2-yl}oxy)propyl]-2,6-ditert-butylphenol Using 2,4,6-Trichloro-[1,3,5]triazine

In a 100 ml of 3-neck round bottom flask, 1.0 g of2,4,6-Trichloro-[1,3,5]triazine is dissolved in 25 ml of anhydroustetrahydrofuran under nitrogen atmosphere. 3.1 ml of triethyl amine isadded. 4.3 g of 2,6-Di-tert-butyl-4-(3-hydroxy-propyl)-phenol istransferred to the round bottom flask under nitrogen atmosphere.Reactants are heated to reflux temperature of tetrahydrofuran (65° C.).The reaction is completed in 15 hours. The crude product thus obtainedis purified to get4-[3-({4,6-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propoxy]-1,3,5-triazin-2-yl}oxy)propyl]-2,6-ditert-butylphenol.

Example 21: Synthesis of4-[3-({4,6-bis[(4-anilinophenyl)(1,3-dimethylbutyl)amino]-1,3,5-triazin-2-yl}oxy)propyl]-2,6-ditert-butylphenol Using2,4,6-Trichloro-[1,3,5]triazine

In a 100 ml of 3-neck round bottom flask, 1.0 g of2,4,6-Trichloro-[1,3,5]triazine is dissolved in 25 ml of anhydroustetrahydrofuran under nitrogen atmosphere. Flask is kept in ice bathmaintained at 0° C. using salt. 3.1 ml of triethyl amine is added. 1.6 gof 2,6-Di-tert-butyl-4-(3-hydroxy-propyl)-phenol is transferred to theround bottom flask under nitrogen atmosphere. It is stirred for 4 hoursat 0° C. Now 3.1 g ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine is transferred tothe round bottom flask under nitrogen atmosphere. Reactants are heatedto reflux temperature of tetrahydrofuran (65° C.). The reaction iscompleted in 15 hours. The crude product thus obtained is purified toget4-[3-({4,6-bis[(4-anilinophenyl)(1,3-dimethylbutyl)amino]-1,3,5-triazin-2-yl}oxy)propyl]-2,6-ditert-butylphenol.

Example 22: Synthesis of4-[3-({4-[(4-anilinophenyl)(1,3-dimethylbutyl)amino]-6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)-propoxy]-1,3,5-triazin-2-yl}oxy)propyl]-2,6-ditert-butylphenolUsing 2,4,6-Trichloro-[1,3,5]triazine

In a 100 ml of 3-neck round bottom flask, 1.0 g of2,4,6-Trichloro-[1,3,5]triazine is dissolved in 25 ml of anhydroustetrahydrofuran under nitrogen atmosphere. Flask is kept in ice bathmaintained at 0° C. using salt. 3.1 ml of triethyl amine is added. 1.7 gof N-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine is transferredto the round bottom flask under nitrogen atmosphere. It is stirred for 4hours at 0° C. Now 3.0 g of2,6-Di-tert-butyl-4-(3-hydroxy-propyl)-phenol is transferred to theround bottom flask under nitrogen atmosphere. Reactants are heated toreflux temperature of tetrahydrofuran (65° C.). The reaction iscompleted in 15 hours. The crude product thus obtained is purified toget4-[3-({4-[(4-anilinophenyl)(1,3-dimethylbutyl)amino]-6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)-propoxy]-1,3,5-triazin-2-yl}oxy)propyl]-2,6-ditert-butylphenol.

Example 23: Synthesis of N, N′,N″-Tris-(1,3-dimethyl-butyl)-N, N′,N″-tris-(4-phenylamino-phenyl)-propane-1,2,3-triamine Using1,2,3-Trichloro-propane

In a 100 ml of 3-neck round bottom flask, 1.0 g of1,2,3-Trichloro-propane is dissolved in 25 ml of anhydrous toluene undernitrogen atmosphere. 3.0 ml of triethyl amine is added. 5.8 g ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine is transferred tothe round bottom flask under nitrogen atmosphere. Reactants are heatedto reflux temperature of toluene (110° C.). The reaction is completed in20 hours. The crude product thus obtained is purified to get 4.8 g of N,N′,N″-Tris-(1,3-dimethyl-butyl)-N, N′,N″-tris-(4-phenylamino-phenyl)-propane-1,2,3-triamine.

Example 24: Synthesis of4-[3-({3,5-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propoxy]pentyl}oxy)propyl]-2,6-ditert-butylphenolUsing 1, 2,3-Trichloro-propane

In a 100 ml of 3-neck round bottom flask, 1.0 g of1,2,3-Trichloro-propane is dissolved in 25 ml of anhydrous toluene undernitrogen atmosphere. 3.2 ml of triethyl amine is added. 5.7 g of2,6-Di-tert-butyl-4-(3-hydroxy-propyl)-phenol is transferred to theround bottom flask under nitrogen atmosphere. Reactants are heated toreflux temperature of toluene (110° C.). The reaction is completed in 20hours. The crude product thus obtained is purified to get4-[3-({3,5-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propoxy]pentyl}oxy)propyl]-2,6-ditert-butylphenol.

Example 25: Synthesis of2,6-Di-tert-butyl-4-[3-(2-[(1,3-dimethyl-butyl)-(4-phenylamino-phenyl)-amino]-]-{[(1,3-dimethyl-butyl)-(4-phenylamino-phenyl)-amino]-methyl}-ethoxy)-propyl]-phenolUsing 1,2,3-Trichloro-propane

In a 100 ml of 3-neck round bottom flask, 1.0 g of1,2,3-Trichloro-propane is dissolved in 25 ml of anhydroustetrahydrofuran under nitrogen atmosphere. Flask is kept in ice bathmaintained at 0° C. using salt. 3.2 ml of triethyl amine is added. 3.1 gof N-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine is transferredto the round bottom flask under nitrogen atmosphere. It is stirred for10 hours at 0° C. Now 1.5 g of2,6-Di-tert-butyl-4-(3-hydroxy-propyl)-phenol is transferred to theround bottom flask under nitrogen atmosphere. Reactants are heated toreflux temperature of toluene (110° C.). The reaction is completed in 5hours. The crude product thus obtained is purified to get2,6-Di-tert-butyl-4-[3-(2-[(1,3-dimethyl-butyl)-(4-phenylamino-phenyl)-amino]-1-{[(1,3-dimethyl-butyl)-(4-phenylamino-phenyl)-amino]-methyl}-ethoxy)-propyl]-phenol.

Example 26: Synthesis of4-[3-({3-[(4-anilinophenyl)(1,3-dimethylbutyl)amino]-5-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propoxy]pentyl}oxy)propyl]-2,6-ditert-butylphenolUsing 1,2,3-Trichloro-propane

In a 100 ml of 3-neck round bottom flask, 1.0 g of1,2,3-Trichloro-propane is dissolved in 25 ml of anhydrous toluene undernitrogen atmosphere. Flask is kept in ice bath maintained at 0° C. usingsalt. 3.2 ml of triethyl amine is added. 3.0 g of2,6-Di-tert-butyl-4-(3-hydroxy-propyl)-phenol is transferred to theround bottom flask under nitrogen atmosphere. It is stirred for 10 hoursat 0° C. Now 1.6 g ofN-(1,3-Dimethyl-butyl)-N′-phenyl-benzene-1,4-diamine is transferred tothe round bottom flask under nitrogen atmosphere. Reactants are heatedto reflux temperature of toluene (110° C.). The reaction is completed in5 hours. The crude product thus obtained is purified to get4-[3-({3-[(4-anilinophenyl)(1,3-dimethylbutyl)amino]-5-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propoxy]pentyl}oxy)propyl]-2,6-ditert-butylphenol.

The performance of the compound of the present invention (Example 2) wasassessed by measuring the oxidative induction time of stabilized samplesof vegetable oil at elevated temperature (150° C.) and under high oxygenpressure (500 psi). This is a standard test method in the lubricantindustry and is described in ASTM D 6186. Testing was conducted inbiolubricant base oils, canola and soybean oil. These base oils differmainly in their content of polyunsaturated fatty acids which areespecially unstable to oxidation, with soybean oil having the highestconcentration and hence the lowest inherent oxidative stability.

The performance of the compound in Example 2 was assessed vs. thecommercial antioxidant Irganox® L 135 (CAS No. 125643-61-0, BASF) as acontrol.

The testing results are summarized in Table 1. The antioxidant ofExample 2 outperformed the commercial control Irganox® L 135 by asignificant margin in both bio-based oils.

In canola oil, the performance enhancement factor for compound ofExample 2 over the commercial antioxidant was approximately 3× (compareresults for 0.5% Example 2 vs. 1.5% Irganox® L 135). At higher treatlevels, the new antioxidant provided a level of performance that couldnot be achieved with state-of-the-art commercial antioxidants. Thisresult once again suggests that the new antioxidant of this instantinvention may enable the use of bio-lubricants based on canola oil inhigher performance applications from which they are currently excluded.

In the more oxidatively unstable soybean oil, the performanceenhancement factor for compound of Example 2 over the commercialantioxidant was approximately 1.5× (compare results for 1.0% Example 2with 1.5% Irganox® L 135).

TABLE 1 Performance of antioxidants in biolubricant oils: canola andsoybean oils. Oxidative Induction Time (min), 150° C., 500 psi O₂,Canola oil Soybean oil Additive 0.5% 1.0% 1.5% 0.5% 1.0% 1.5% Example 231.3 34.1 44.0 12.3 17.3 24.1 Irganox ® L 135 15.7 23.5 31.2 9.8 14.917.6

The performance of the present invention was also assessed in esteroils. These synthetic base oils are classified as part of Group V baseoil groups according to American Petroleum Institute (API 1509, AppendixE). Synthetic esters are used in different lubricant formulations toimprove the properties. The test method described for vegetable andbiolubricant oils, ASTM D 6186 method was used to test and compare theperformance of the present invention in ester oils of different kinds.The test temperature was 180° C. and oxygen pressure was 500 psi. Bothtrimethylolpropane (TMP) based polyols ester oil (TruVis Teknor 810TMP)and neopentyl glycols (NPG) polyols ester oil (HATCOL 2957) were added1000 ppm of antioixdant and tested using ASTM D6186 method at 180° C.and 500 psi O₂.

The performance of the compounds in Examples 2, 13, and 16 was assessedvs. the commercial antioxidant Irganox® L 135 (CAS No. 125643-61-0,BASF) as a control in TMP and NPG oils.

The testing results are summarized in Tables 2 and 3. The antioxidantsof the present invention Examples 2, 13, and 16 outperformed thecommercial control Irganox® L 135 by a significant margin in both esteroils.

TABLE 2 Performance of antioxidants in Group V oils: Polyolester oil,TMP based oil Oxidative Induction Time (min), 180° C., 500 psi O₂ Oil:TMP polyol ester oil, Additive 1000 ppm Example 2 104.8 Irganox ® L 13518.3

In synthetic polyolester oil (TMP base oil), the performance enhancementfactor for compound of Example 2 over the commercial antioxidant wasapproximately 5.7× (Table 2). This result once again suggests that thenew antioxidant of this instant invention may enable the use ofsynthetic base lubricant oil in higher performance applications fromwhich they are currently excluded.

TABLE 3 Performance of antioxidants in Group V oils: Polyolester oil,NPG based oil Oxidative Induction Time (min), 180° C., 500 psi O₂ Oil:NPG polyol ester oil Additive 1000 ppm Example 2  59.5 Example 13 60.6Example 16 61.4 Irganox ® L 135 12.2

Table 3 shows all three antioxidants of the present invention outperformover the commercial antioxidant in another type of polyolester, NPGbased oil. The performance enhancement factor was approximately 5×.

The performance of the present invention compound (Example 2) wasassessed by measuring the oxidative induction time (OIT) of polyolefinsamples at elevated temperature (170° C.) and under high oxygen pressure(500 psi). This is a standard test method and is described in ASTM D5885. The performance of the compound in Example 2 was assessed vs. thecommercial antioxidant Irganox® 1010 (CAS No. 6683-19-8) as a control.The stabilized polyolefin samples were prepared by extrudingpolypropylene (PH350, LyondellBasell) with 1000 ppm antioxidant, 100 ppmof calcium stearate (CaS) (CAS No. 1592-23-0) and 1000 ppm of Irganox168 (CAS No. 31570-04-4) using a Randcastle extruder (RCP-0250) at 250°C. in into mini size pellets. These mini pellets were used to test andcompare performance of antioxidants in polyolefin.

The testing results are summarized in Table 3. The antioxidant ofExample 2 outperformed the commercial control Irganox® 1010 by asignificant margin (3×) in stabilized polypropylene.

TABLE 4 Performance of antioxidants in polyolefin: polypropylene.Oxidative Induction Time (min), ASTM D5185 Method 170° C., 500 psi O₂Sample: Polypropylene (PP) Additive* 1000 ppm Example 2 24.1 Irganox ®1010 8.4 *formulation: antioxidant 1000 ppm + calcium stearate 1000ppm + 1000 ppm Irganox ® 168

The OIT of the stabilized polyolefin samples (polypropylene,(PP)) wasdetermined according to the procedure of ASTM D 5885. The system used tomeasure the OIT was TA Instruments Model Q10. The sample and thereference are heated at a constant rate of 20° C./min to reach 170° C.The heating was held isothermally after reaching 170° C. The zero timewas taken when the heating was started. The sample cell was purged withoxygen and pressurized to 500 psi of oxygen. The end of the inductionperiod was signaled by an abrupt increase in the sample's evolved heatas recorded by the instrument. OIT was measured from the start ofisothermal conditions to the inflection point of the exothermic peak.

What is claimed is:
 1. A method of making a mixture of compounds havingthe following structure:

wherein R″ is represented by the following formula:

the method comprising combining a mixture of amine compounds having thefollowing formula:

with an equimolar amount of a phenol compound having the followingformula:

wherein R is —H or OH or OCH3 or Cl.
 2. The method of claim 1, where thephenol compound is 3-(3,5-ditert-butyl-4-hydroxyphenyl)propionylchloride and a mixture of at least two amines selected fromN-phenyl-1,4-phenylene-diamine;N1-isopropyl-N4-phenylbenzene-1,4-diamine;N1-(1,3-dimethylbutyl)-N4-phenylbenzene-1,4-diamine;N1-(1,4-dimethylpentyl)-N4-phenylbenzene-1,4-diamine;N-sec-octyl-N′-phenyl-p-phenylenediamine.
 3. A method for preventingoxidation in an oxidizable material, comprising combining the oxidizablematerial with a mixture of compounds having the following structuredformulae:


4. The method of claim 3, wherein the oxidizable material is bio-oil ormodified bio-oil, vegetable oil and/or animal fat, polyolesters,petroleum based Group I, II, III, IV, and V oil, or mixture thereof;lubricants, biolubricants, biobased lubricants, plastics, bioplastics,polyolefins, nylons, polyamides, elastomers, thermoplastic elastomers,polymers copolymers, gasoline, kerosene, diesel, and biodiesel.
 5. Astabilized lubricant composition comprising (a) a lubricant or a mixtureof lubricants, (b) a mixture of compounds according to claim
 1. 6. Thestabilized lubricant composition of claim 5, wherein the antioxidantcomposition is in an amount 0.05% to 5% by weight of the lubricantcomposition.
 7. The stabilized lubricant composition of claim 6, furthercontaining at least one lubricant additive in an amount 0.05% to 5% byweight of the lubricant composition selected from the group consistingof anti-wear additives, metal deactivating agents, antioxidants,detergents, rust inhibitors, friction modifiers, viscosity modifiers,pour point depressants, corrosion inhibitors, demulsifying regents,anti-foaming agents.
 8. A stabilized lubricant composition of claim 6,wherein the lubricant is selected from the group consisting ofpetroleum-based oils, synthetic oils, biolubricant oils, and biobasedoils, and mixture thereof.
 9. A method of forming a stabilized lubricantcomposition, comprising combining a lubricant or mixture of lubricantsto form a lubricant composition consisting essentially of: a) a mixtureof compounds according to claim 1; b) at least one additive selectedfrom the group consisting of: anti-wear additives, metal deactivatingagents, antioxidants, detergents, rust inhibitors, friction modifiers,viscosity modifiers, pour point depressants, corrosion inhibitors,demulsifying regents, anti-foaming agents, to thereby form a lubricantcomposition, wherein the concentration of the first antioxidant isbetween about 0.05% to about 5% by weight of the lubricant compositionand the concentration of the first additive is between about 0.05% andabout 5% by weight of the lubricant composition.
 10. A stabilized fuelcomposition comprising: a) a mixture of compounds according to claim 1;b) one or more of an anti-corrosion, anti-foaming, viscosity modifier,pour point depressants, phenolic and aminic antioxidant; c) a fuelselected from petroleum, gasoline, kerosene, aviation fuel, diesel, andbiodiesel.